Polyoxometalate materials, metal-containing materials, and methods of use thereof

ABSTRACT

The invention relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H 5 PV 2 Mo 10 O 40 ; K 5 Si(H 2  O)Mn III W 11 O 39 ; K 4 Si(H 2 O)Mn IV W 11 O 39 ; or K 5 Co III W 12 O 40 . The invention further relates to a method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of the present invention with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment. The invention further relates to a method for removing a contaminant from an environment, comprising contacting a polyoxometalate powder or a polyoxometalate coating with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment. The invention further relates to a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof. The invention further relates to a method for removing a contaminant from an environment, comprising contacting a modified material with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment, wherein the modified material comprises (1) a material and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate. The invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises (1) a material comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate. The invention further relates to an article comprising the modified material of the present invention.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority upon U.S. provisionalapplication Ser. No. 60/158,952, filed on Oct. 12, 1999, and thecontents of which are herein incorporated by this reference in theirentirety.

FIELD OF THE INVENTION

[0002] The present invention relates to materials containing apolyoxometalate or a metal compound, wherein the metal compound is not apolyoxometalate. The invention further relates to methods for removing acontaminant from an environment by contacting the environment with apolyoxometalate material or a non-polyoxometalate material.

BACKGROUND OF THE INVENTION

[0003] Decreasing the potential danger of contaminants from theenvironment has long been a significant issue. For example, the removalof offensive odors originating from cigarette smoke, sweat, exhaustgases, and rotten food in the work place, the home, and elsewhere wouldbe quite beneficial to the public-at-large. Additionally, materials thatcan remove highly toxic contaminants, such as chemical warfare agents(CWAs), from the environment can ultimately reduce a soldier's exposureto the agent. Examples of materials that would be useful include creams,powders, coatings, and fabrics.

[0004] Creams, also referred to as topical skin protectants (TSPs), havebeen developed to protect soldiers from the threat of dermal exposure tochemical warfare agents. TSPs require an inert material which can beapplied on the skin in a thin layer to form an antipenetrant barrier toCWAs or other contact irritants that will not interfere excessively withnormal skin functions. A preferred TSP affords protection against CWAsand other toxic or irritating materials in all of the forms in whichthey might be encountered (e.g., liquid, aerosolized liquid and vapor).Perhaps the best-known vesicant CWA is 2,2′-dichlorodiethylsulfide (alsoknown as “HD” or “sulfur mustard”), which was first used during WorldWar I. Improved TSPs, however, are needed for protecting militarypersonnel and civilians from percutaneous exposure to CWAs andprotecting the skin from contact dermatitis arising from other sourcesas well.

[0005] U.S. Pat. No. 5,607,979 to McCreery discloses topical creamsformed from about 35% to about 50% fine particulates of certainpoly(tetrafluoroethylene) (PTFE) resins dispersed in perfluorinatedpolyether oils having viscosities from about 20 cSt to about 350 cSt.The creams afford protection against chemical warfare agents such assulfur mustard (HD), lewisite (L), sulfur mustard/Lewisite mixtures(HL), pinacolyl methylphosphonofluoridate (soman or GD), thickened soman(TGD) and O-ethyl-S-2-diisopropylaminoethyl methylphosphonothiolate(VX). These creams, however, can only provide limited exposure to a CWAfor a short period of time. Furthermore, the creams cannot convert theCWA to an inactive form, which will reduce the overall toxicity of theCWA.

[0006] Thus, there is a need for a material, which is also referred toherein as a support, that can remove a contaminant from the environmentfor an extended period of time. The incorporation of a polyoxometalate(herein referred to as “POM”) into a material such as a cream, coating,powder, or fabric, is one approach to removing a contaminant from anenvironment. Gall et al. (Chem. Mat. 8, pp. 2523-2527, 1996) disclosethe immobilization of H₅PV₂Mo₁₀O₄₀ on carbon cloth in order to determinethe ability of H₅PV₂Mo₁₀O₄₀ to remove sulfur containing compounds fromtoluene. Johnson et al. (Proc. ERDEC Sci. Conf. Chem. Biol. Def. Res.,1998, pp. 393-399) disclose suspending H₅PV₂Mo₁₀O₄₀;K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O )Mn^(IV)W₁₁O₃₉; or K₅Co^(III)W₁₂O₄₀ ina perflouropolyether barrier cream to determine the creams ability todetect the presence of mustard gas. Johnson et al., however, is notconcerned with the removal of the mustard gas from the gas phase.

[0007] The prior art also discloses the incorporation ofpolyoxometalates into powders and coatings. For example, U.S. Pat. No.5,356,469 to Curcio et al. disclose a metal pigment composition suitablefor the formation of a coating composition. The coating composition iscomposed of a solvent, a metal pigment, at least one phosphosilicatepigment, and at least one heteropoly anion. The metal pigment particlespossess increased stability against attack by water. Japanese patentapplication number 4054127 to Terumo Corp. discloses the use ofheteropoly acid salts as anti-tumor agents. The heteropoly acid saltscan be administered in the form of a powder or suspended in solution.Although the prior art discloses a number of different applications ofpolyoxometalate powders or coatings, the art does not disclose the useof a powder or coating containing a polyoxometalate to remove acontaminant from the environment.

[0008] In light of the above, it would be very desirable to have anarticle and a method of using an article for the removal of toxic and/ormalodorous compounds without adding stoichiometric amounts of additivesor compounds to the article. The present invention solves such a need inthe art while providing surprising advantages. The present inventionherein incorporates a polyoxometalate (POM) into a material such as atopical carrier, powder, or coating, which greatly increases the abilityof the to remove a contaminant from the environment. The presentinvention also incorporates a metal compound, wherein the metal compoundis not a polyoxometalate, into a in order to remove a contaminant fromthe environment.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009]FIG. 1 shows the consumption of oxygen and formation of CEESO as afunction of time.

[0010]FIG. 2 shows CEESO formation as a function of time using1Au/2Cu/3NO₃; 2Cu/3NO₃; and 1Au/3NO₃.

SUMMARY OF THE INVENTION

[0011] In accordance with the purpose(s) of this invention, as embodiedand broadly described herein, this invention, in one aspect, relates toa polyoxometalate topical composition for removing a contaminant from anenvironment, comprising a topical carrier and at least onepolyoxometalate, with the proviso that the polyoxometalate is notH₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O )Mn^(IV)W₁₁O₃₉; orK₅Co^(III)W₁₂O₄₀.

[0012] The invention further relates to a method for removing acontaminant from an environment, comprising contacting thepolyoxometalate topical composition of the present invention with theenvironment containing the contaminant for a sufficient time to removethe contaminant from the environment.

[0013] The invention further relates to a method for removing acontaminant from an environment, comprising contacting a polyoxometalatepowder or a polyoxometalate coating with the environment containing thecontaminant for a sufficient time to remove the contaminant from theenvironment.

[0014] The invention further relates to a modified polyoxometalate,wherein the modified polyoxometalate comprises the admixture of (1) apolyoxometalate and (2) a cerium compound, a silver compound, a goldcompound, a platinum compound, or a combination thereof.

[0015] The invention further relates to a method for removing acontaminant from an environment, comprising contacting a modifiedmaterial with the environment containing the contaminant for asufficient time to remove the contaminant from the environment, whereinthe modified material comprises (1) a material and (2) a metal compoundcomprising a transition metal compound, an actinide compound, alanthanide compound, or a combination thereof, wherein the metalcompound is not a polyoxometalate.

[0016] The invention further relates to a modified material for removinga contaminant from an environment, wherein the modified materialcomprises (1) a material comprising a topical carrier, a powder, acoating, or a fabric, and (2) a metal compound comprising a transitionmetal compound, an actinide compound, a lanthanide compound, or acombination thereof, wherein the metal compound is not apolyoxometalate.

[0017] The invention further relates to an article comprising themodified of the present invention.

[0018] Additional advantages of the invention will be set forth in partin the description which follows, and in part will be obvious from thedescription, or may be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combinations. It is to be understood that both theforegoing general description and the following detailed description areexemplary and explanatory only and are not restrictive of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention may be understood more readily by referenceto the following detailed description of preferred embodiments of theinvention and the Examples included therein.

[0020] Before the present methods and articles are disclosed anddescribed, it is to be understood that this invention is not limited tospecific synthetic methods or to particular formulations, as such may,of course, vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only andis not intended to be limiting.

[0021] In this specification and in the claims which follow, referencewill be made to a number of terms which shall be defined to have thefollowing meanings:

[0022] The singular forms “a,” “an” and “the” include plural referentsunless the context clearly dictates otherwise.

[0023] “Optional” or “optionally” means that the subsequently describedevent or circumstance may or may not occur, and that the descriptionincludes instances where said event or circumstance occurs and instanceswhere it does not.

[0024] In accordance with the purpose(s) of this invention, as embodiedand broadly described herein, this invention, in one aspect, relates toa polyoxometalate topical composition for removing a contaminant from anenvironment, comprising a topical carrier and at least onepolyoxometalate, with the proviso that the polyoxometalate is notH₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; orK₅Co^(III)W₁₂O₄₀.

[0025] The invention further relates to a modified polyoxometalate,wherein the modified polyoxometalate comprises the admixture of (1) apolyoxometalate and (2) a cerium compound, a silver compound, a goldcompound, a platinum compound, or a combination thereof.

[0026] The invention further relates to a modified material for removinga contaminant from an environment, wherein the modified materialcomprises (1) a material comprising a topical carrier, a powder, acoating, or a fabric, and (2) a metal compound comprising a transitionmetal compound, an actinide compound, a lanthanide compound, or acombination thereof, wherein the metal compound is not apolyoxometalate.

[0027] The invention further relates to an article comprising themodified material of the present invention.

[0028] Many polyoxometalates known in the art can be used in the presentinvention to remove a contaminant from an environment. Polyoxometalatesare also referred to in the art as heteropoly compounds, heteropolyacids, isopoly compounds, and isopoly acids, which are subsets ofpolyoxometalates. Examples of polyoxometalates useful in the presentinvention are disclosed in Pope, M. T. in Heteropoly and IsopolyOxometalates, Springer Verlag, 1983, and Chemical Reviews, vol. 98, no.1, pp. 1-389, 1998, which are incorporated by this reference in theirentirety.

[0029] The selection of the polyoxometalate used in the presentinvention is dependent upon the contaminant or contaminants to beremoved from the environment. In one embodiment, the polyoxometalate hasthe formula 1 of [V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A],wherein M is at least one f-block element or d-block element having atleast one d-electron, wherein M is not vanadium, molybdenum, tungsten,niobium, or tantalum; X is at least one p-, d-, or f-block element,wherein X is not oxygen; k is from 0 to 30; m is from 0 to 160; n isfrom 0 to 160; o is from 0 to 10; p is from 0 to 10; q is from 0 to 30;r is from 0 to 30; s is sufficiently large that y is greater than zero;and y is greater than zero, wherein the sum of k, m, n, o, and p isgreater than or equal to four; and the sum of k, m, and q is greaterthan zero, and A is one or more different counterions. In oneembodiment, s is from 19 to 460. The charge on the POM, y, is dictatedby the values of k, m, n, o, p, q, r and s. The p-, d-, and f-blockelements can exist in any oxidation state.

[0030] Generally, M can be any d-block element having at least oned-electron or f-block element having at least one f-electron. Typically,M comprises titanium, chromium, manganese, cobalt, iron, nickel, copper,rhodium, silver, palladium, platinum, mercury, ruthenium, cerium, oreuropium. In a preferred embodiment, M comprises manganese, cobalt, orruthenium In another embodiment, X comprises phosphorus, silicon,aluminum boron, cobalt, zinc, or iron. When the polyoxometalate has theKeggin structure XM₁₂, then it is possible for X and at least one M tobe the same d- or f-block element. Not wishing to be bound by theory, itis believed that the metal ion M of the polyoxometalate of the presentinvention is responsible for removing the contaminant from the gasphase, while X, when present, provides structural integrity to thepolyoxometalate.

[0031] In one embodiment, the sum of k and q is greater than or equal toone, the sum of k, m, n, o, p, and q is 12, and s is 40. In yet anotherembodiment, k is not zero. In another embodiment, q is not zero.

[0032] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X^(g+)V_(b) ^(j+M) _(c)^(h+Z) _(12−b−c) ^(i+)O_(x)]^(u−)[A], wherein X is at least one p, d-,or f-block element; g is greater than or equal to 2; M is at least onef-block element or d-block element having at least one d-electron,wherein M is not vanadium; h is from 1 to 7; i is from 5 to 6; j is from4 to 5; x is 39 or 40; Z is tungsten, molybdenum, niobium, or acombination thereof; b is from 0 to 6; c is from 0 to 6; u is from 3 to9; and A is a counterion. The values of u, x, i b, c, g, h, and j willvary depending upon the selection of X, M, and Z. The variables arerelated to one another and can be derived by the following formula:

u=2(x)−i(12−b−c)−g−c(h)−b(j)

[0033] The values of h, i and j are average charges, and depend upon theselection and number of X, M, Z, and V present in the POM. For example,when Z is Nb⁺⁵ and Nb⁺6 (i.e., two Nb atoms present in the POM), thevalue of i+ is 5.5.

[0034] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X^(g+)V_(b)^(j+)Z_(12−b) ^(i+)O₄₀]^(u−)[A], where X is at least one phosphorus,silicon, aluminum, boron, zinc, cobalt, or iron; b is from 1 to 6, and uis from 3 to 9.

[0035] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the structure [X^(g+)M_(c)^(h+)Z_(12−c) ^(i+)O₄₀]^(u−)[A], wherein X is at least one phosphorus,silicon, aluminum, boron, zinc, cobalt, or iron; c is from 1 to 6, and uis from 3 to 9.

[0036] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X₂ ^(r+)V_(u) ^(s+)M_(v)^(t+)Z_(18−u−v) ^(y+)O_(z)]^(w−)[A], wherein X is at least one p-, d-,or f-block element; r is greater than or equal to 1; M is at least onef-block element or d-block element having at least one d-electron,wherein M is not vanadium; t is from 1 to 7; s is from 4 to 5; Z istungsten, molybdenum niobium, or a combination thereof; u is from 0 to9; v is from 0 to 9; y is from 5 to 6; z is 61 or 62; w is greater thanor equal to 4; and A is a counterion. Similar to the formula above, thevalues of r, s, t, u, v, w, y, and z, will vary depending upon theselection of X, M, and Z. The variables are related to one another andcan be derived by the following formula:

w=2(z)−y(18−u−v)−2r−v(t)−u(s)

[0037] The values of r, s, t, and y are also average charges, and dependupon the selection and number of X, M, Z, and V atoms present in thePOM.

[0038] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X₂ ^(r+)V_(u)^(s+)Z_(18−u) ^(y+)O₆₂]^(w−)[A], wherein X is at least one phosphorus,sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; u is from 1 to9; and w is greater than or equal to 4.

[0039] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X₂ ^(r+)M_(v)^(t+)Z_(18−v) ^(y) ⁺O₆₂]^(w−)[A], wherein X is at least one phosphorus,sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; v is from 1 to9; and w is greater than or equal to 4.

[0040] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [YV_(p)Z_(12−p)O₄₀][A],wherein Y is phosphorus, silicon, or aluminum; Z is tungsten ormolybdenum; p is from 1 to 6, and A is a counterion. In one embodiment,Y is phosphorus and Z is molybdenum. In one embodiment, Y is phosphorusand Z is tungsten. In one embodiment, Y is silicon and Z is molybdenum.In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Yis aluminum and Z is tungsten. In one embodiment, Y is aluminum and Z ismolybdenum.

[0041] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X^(g+)V_(b)M^(h+)_(c)Z_(12−b−c)O₄₀]^(u−)[A], wherein X is at least one p-, d-, or f-blockelement; g+ is the charge of X; M is at least one f-block element ord-block element having at least one d-electron, wherein M is notvanadium; h+ is the charge of M; Z is tungsten, molybdenum, niobium, ora combination thereof; b is from 0 to 6; c is from 0 to 6, wherein thesum of b and c is greater than or equal to one; u is greater than 3; andA is a counterion.

[0042] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula[X^(g+)V_(b)Z_(12−b)O₄₀]^(u−)[A], wherein X is at least one phosphorus,silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten,molybdenum, niobium, or a combination thereof; b is from 1 to 6; and uis greater than 3.

[0043] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X^(g+)M^(h+)_(c)Z_(12−c)O₄₀]^(u−)[A], wherein X is at least one phosphorus, silicon,aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten,molybdenum, niobium, or a combination thereof; M^(h+) is at least onef-block element or d-block element having at least one d-electron; c isfrom 1 to 6; and u is greater than 3.

[0044] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X^(i+) ₂V_(u)M^(j+)_(v)Z_(18−u−v)O₆₂]^(w−)[A], wherein X is at least one p-, d-, or f-blockelement; i+ is the charge of X; M is at least one d- or f-block element,wherein M is not vanadium; j+ is the charge of M; Z is tungsten,molybdenum, niobium, or a combination thereof, u is from 0 to 9; v isfrom 0 to 9, wherein the sum of u and v is greater than or equal to one;w is greater than or equal to 4; and A is a counterion.

[0045] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X^(i+)₂V_(u)Z_(18−u)O₆₂]^(w−)[A] wherein X is at least one phosphorus, sulfur,silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten,molybdenum, niobium, or a combination thereof; u is from 1 to 9; and wis greater than or equal to 4.

[0046] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [X^(i+) ₂M^(j+)_(v)Z_(18−v)O₆₂]^(w−)[A] wherein X is at least one phosphorus, sulfur,silicon, aluminum boron, zinc, cobalt, or iron; Z comprises tungsten,molybdenum, niobium, or a combination thereof; M^(j+) is at least one d-or f-block element; v is from 1 to 9; and w is greater than or equal to4.

[0047] In a more specific embodiment, when the polyoxometalate has theformula 1, the polyoxometalate has the formula [YV_(x)Z_(12−x)O₄₀][A],wherein Y is phosphorus, silicon, or aluminum; Z is tungsten ormolybdenum; x is from 1 to 6, and A is a counterion. In one embodiment,Y is phosphorus and Z is molybdenum. In one embodiment, Y is phosphorusand Z is tungsten. In one embodiment, Y is silicon and Z is molybdenum.In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Yis aluminum and Z is tungsten. In one embodiment, Y is aluminum and Z ismolybdenum.

[0048] Polyoxometalates having an organic group, such as an alkyl groupor aryl group, an organosilyl group, or other p- or d-blockorganometallic groups bonded to the POM can also be used in the presentinvention. The organic group can be branched or straight chain alkyl,alkenyl, or alkynyl group or an aryl group of C₁ to C₃₀. The alkyl groupcan also be a polyether or polyol. Not wishing to be bound by theory,the organic group is bonded to the polyoxometalate as depicted in Scheme1, where R is the organic group and Met is generally vanadium,molybdenum, tungsten, niobium, or tantalum.

[0049] The reaction between an alcohol and the polyoxometalate I resultsin the loss of water and the formation of the polyoxometalate II,wherein the organic group is bonded to an oxygen atom of thepolyoxometalate. Any alcohol known in the art can be used in the presentinvention. Examples of alcohol that can be used include, but are notlimited to, methanol, ethanol, or tris(hydroxymethyl)methane. Thepolyoxometalates having organic groups bonded to the POM that aredisclosed in Gouzerh et al., Chem. Rev., 98, pp. 77-111, 1998, which isincorporated by reference in its entirety, are useful in the presentinvention.

[0050] In another embodiment, the polyoxometalate I can be reacted witha compound having the generic formula YL_(o)R_(4−o), wherein Y issilicon, tin, or an other p- or d-block element; L is a leaving group; Ris an organic group, such as an alkyl, alkenyl, or alkynyl group or anaryl group of C₁ to C₃₀; and o is from 1 to 4. Suitable leaving groupsfor L include, but are not limited to, halides and alkoxides. In SchemeI, the oxygen of polyoxometalate I displaces L from YLR₃ to form a newY—O bond. (compound III). Any silyl, tin, or organic derivative of a p-or d-block element known in the art can be used in the presentinvention, provided that the compound has at least one leaving group.

[0051] The counterion A can be any counterion known in the art. Examplesof counterions include, but are not limited to, quaternary ammoniumcation, proton, alkali metal cation, alkaline earth metal cation,ammonium cation, d-block cations, f-block cations, or a combinationthereof. In one embodiment, the polyoxometalate is an acid, wherein thecounterion A is hydrogen (H⁺). In one embodiment, the counterion is a d-or f-block metal complex. In one embodiment, the counterion istrimethyl-triazacyclononane manganese. In another embodiment, thecounterion A is hydrogen, lithium (Li⁺), sodium (Na⁺), potassium (K⁺),or a combination thereof. In another embodiment, A is not hydrogen orpotassium.

[0052] In another embodiment, the polyoxometalate comprises a modifiedpolyoxometalate, wherein the modified polyoxometalate comprises theadmixture of (1) a pre-modified polyoxometalate and (2) a ceriumcompound, a silver compound, a gold compound, a platinum compound, acopper compound, a cobalt compound, or a combination thereof. The term“admixture” can refer to the reaction product between thepolyoxometalate and the cerium compound, silver compound, gold compound,platinum compound, or a combination thereof. For example, the ceriumcompound, silver compound, gold compound, or platinum compound canundergo ion exchange with the counterion of the polyoxometalate. Thecerium compound, silver compound, gold compound, or platinum compoundcan also react with the polyoxometalate by a redox reaction. The term“admixture” can also refer to when the cerium compound, silver compound,gold compound, or platinum compound do not react at all with thepolyoxometalate. For example, the polyoxometalate may absorb the ceriumcompound, silver compound, gold compound, or platinum compound.

[0053] In one embodiment, when the POM is the sodium, lithium, orpotassium salt or the acid form (A is H⁺), the POM can undergo ionexchange with a cerium compound, a silver compound, a gold compound, aplatinum compound, or a combination thereof. For example, Ag₅PV₂Mo₁₀O₄₀is produced by the ion exchange of Na₅PV₂Mo₁₀O₄₀ with a stoichiometricamount AgNO₃. Any of the POMs described above can undergo ion exchangewith a cerium compound, a silver compound, a gold compound, a platinumcompound.

[0054] Depending upon the type, and amounts of POM and cerium compound,silver compound, gold compound, or platinum compound used, the ionexchange reaction may or may not go to completion. When the ion exchangedoes not go to completion, there may be small population of Na⁺, Li⁺,K⁺, or H⁺ in the modified-polyoxometalate. For example, whenH₅PV₂Mo₁₀O₄₀ is admixed with AgNO₃, the resultant POM may be expressedby the formula Ag_(x)H_(5-x)PV₂Mo₁₀O₄₀, where x is from 1 to 5. Here,varying amounts of H⁺ may be present in the POM.

[0055] An example of a cerium compound useful in the present inventionincludes, but is not limited to, (NH₄)₂Ce(NO₃)₆. Examples of silvercompounds useful in the present invention include, but are not limitedto, AgNO₃ and AgClO₄. Examples of gold compounds useful in the presentinvention include, but are not limited to, HAuCl₄ and salts thereof. Anexample of a platinum compound useful in the present invention includes,but is not limited to, H₂PtCl₆.

[0056] In one embodiment, the counterion is cerium, silver, gold,platinum, or a combination thereof. In another embodiment, A is,independently, cerium, silver, gold, or platinum. In another embodiment,A is (1) cerium and silver; (2) cerium and platinum; (3) cerium andgold; or (4) silver and gold.

[0057] In another embodiment, A comprises (1) hydrogen, lithium, sodium,potassium, or a combination thereof, and (2) cerium, silver, gold,platinum, or a combination thereof.

[0058] In one embodiment, (1) the pre-modified polyoxometalate isH₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or acombination thereof, and (2) the cerium compound is (NH₄)₂Ce(NO₃)₆. Inanother embodiment, (1) the pre-modified polyoxometalate isH₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or acombination thereof; (2) the cerium compound is (NH₄)₂Ce(NO₃)₆; and (3)the gold compound is HAuCl₄. In another embodiment, (1) the pre-modifiedpolyoxometalate is H₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀;K₅PV₂Mo₁₀O₄₀, or a combination thereof; (2) the cerium compound is(NH₄)₂Ce(NO₃)₆; and (3) the platinum compound is H₂PtCl₆. In anotherembodiment, (1) the pre-modified polyoxometalate comprises Na₄PVMo₁₁O₄₀;Na₅PV₂Mo₁₀O₄₀; Na₆PV₃Mo₉O₄₀; Na₅H₂PV₄W₈O₄₀; Na₉PV₆Mo₆O₄₀; Na₅CuPW₁₁O₃₉;Na₅CuPW₁₁O₃₉; Na₅MnPW₁₁O₃₉; K₅CoPW₁₁O₃₉; (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂; orK₁₂Cu₃(W₉PO₃₄O)₂, and (2) the gold compound is HAuCl₄. In anotherembodiment, (1) the pre-modified polyoxometalate is Na₅PV₂Mo₁₀O₄₀ and(2) the silver compound is AgNO₃, AgClO₄, or a combination thereof.

[0059] In another embodiment, the polyoxometalate comprises K₈Co₂W₁₁O₃₉;K₈SiCoVW₁₀O₃₉; K₇SiCoVW₁₀O₃₉; Na₈Co₂W₁₁O₃₉; Ag₅PV₂Mo₁₀O₄₀; Ag₆PV₃Mo₉O₄₀;Ag₈CoVW₁₁O₄₀; Ag₁₂Ce(PW₁₁O₃₉)₂; Na₁₂Ce(PW₁₁O₃₉)₂; K₁₂Ce(PW₁₁O₃₉)₂;Na₅PCuW₁₁O₃₉; H₆PV₃Mo₉O₄₀; or K₅Cu^(II)PW₁₁O₃₉. In another embodiment,the polyoxometalate is not H₆PV₃Mo₉O₄₀.

[0060] Not wishing to be bound by theory, it is believed that somecounterions of the present invention can be reduced to the correspondingmetal when the polyoxometalate contacts the contaminant. For example,when the cation is Ag⁺¹ or Au⁺³, these cations can be reduced to silvermetal or Au⁺¹, respectively, depending upon the contaminant that is tobe removed. Thus, the counterion A can exist in multiple valence states.

[0061] The phrase “metal compound” refers to one or more transitionmetal compounds, actinide compounds, lanthanide compounds, or acombination thereof. When the metal compound is only one compound, thenthe material is directly treated with the metal compound usingtechniques described below. When the metal compound is composed of twoor more compounds, the material can be sequentially treated with thecompounds, or alternatively, the metal compounds can be admixed prior totreating the material with the metal compounds. Depending upon the metalcompounds that are selected, the metal compounds may react with oneanother to form a new species, or they may not react at all with eachother to produce a composition or mixture. Materials that contain ametal compound of the present invention are referred to herein as“non-POM materials.”

[0062] In one embodiment, the metal compound comprises a ceriumcompound, a gold compound, a platinum compound, a silver compound, or acombination thereof. Any of the cerium compounds, gold compounds,platinum compounds, or silver compounds listed above can be used as themetal compound. In another embodiment, the metal compound is a ceriumcompound and a platinum compound, preferably (NH₄)₂Ce(NO₃)₆ and H₂PtCl₆,respectively. In another embodiment, the metal compound is a ceriumcompound and a gold compound, preferably (NH₄)₂Ce(NO₃)₆ and HAuCl₄,respectively. In another embodiment, the metal compound is a silvercompound and a gold compound, preferably AgNO₃ and/or AgClO₄ and HAuCl₄,respectively. In an other embodiment, the metal compound is a ceriumcompounds, preferably (NH₄)₂Ce(NO₃)₆.

[0063] In another embodiment, the metal compound comprises (1) gold,copper, and nitrate; (2) gold, iron, and nitrate; (3) gold, manganese,and nitrate; (4) gold, titanium, and nitrate; (5) gold, cobalt, andnitrate; (6) gold and nitrate; (7) copper and nitrate; (8) iron andnitrate; (9) gold, vanadium, and nitrate; (10) gold, nickel, andnitrate; (11) gold, silver, and nitrate; or (12) gold, chloride, andnitrate. In a preferred embodiment, the metal compound comprises gold,chloride, and nitrate. In another embodiment, the metal compoundcomprises mixing (NEt₄)AuCl₂ with varying amounts of CuSO₄, MnSO₄,VOSO₄; Ti(SO₄)₂, Fe₂(SO₄)₃, NiSO₄, ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄,Pd(NO₃)₄, Na₂SO₃, and/or NBu₄NO₃. In another embodiment, the metalcompound is produced by mixing (NEt₄)AuBr₂ and NBu₄NO₂.

[0064] When the metal compound comprises two or more compounds, thecompounds can be admixed using techniques known in the art. In oneembodiment, the metal compound can be produced by admixing two or moremetal salts. The anion of the salt can be any anion known in the art.Examples of anions include, but are not limited to, sulfate, carbonate,acetate, nitrate, chloride, and stearate. In one embodiment, when two ormore; compounds are used to produce the metal compound, the compoundsare mixed in the presence of a solvent, preferably an organic solvent.In one embodiment, After the compounds have been sufficiently admixed,the solvent is removed, and the metal compound is optionally dried. Inone embodiment, the drying step is by vacuum.

[0065] Any POM or metal compound of the present invention can beincorporated into a material in order to remove a contaminant from theenvironment. Examples of materials include, but are not limited to, atopical carrier, a coating, a powder, or a fabric. As described above, amaterial as used herein refers to a support that holds the POM or metalcompound.

[0066] In one embodiment, the polyoxometalate and the metal compound canbe incorporated sequentially into the material In one embodiment, thepolyoxometalate is incorporated into the material followed by theincorporation of the metal compound into the material In anotherembodiment, the metal compound is incorporated into the materialfollowed by the incorporation of the polyoxometalate into the material

[0067] A wide variety of topical carriers can be used in the presentinvention. Suitable topically acceptable pharmaceutical carriers arethose which typically are used in the topical application ofpharmaceuticals and cosmetics. Examples of such carriers include, butare not limited to, lotions, creams, ointments, and gels. Topicalcarriers are also referred to in the art as barrier creams and topicalskin protectants. Any of the topical carriers disclosed in U.S. Pat. No.5,607,979 to McCreery can be used in the present invention, which isincorporated by reference in its entirety. In one embodiment, thetopical carrier comprises a perfluorinated polymer. In anotherembodiment, the topical carrier comprises a perfluoropolyether. Anexample of a perfluoropolyether (PFPE) useful in the present inventionhas the general formula CF₃O[—CF(CF₃)CF₂O—]_(x)(—CF₂O—)_(y)CF₃). In oneembodiment, the topical carrier comprises a perflourinated polymer andone or more unfluorinated polymers. In another embodiment, the topicalcarrier comprises a perfluoropolyether and one or more unfluorinatedpolyethers.

[0068] In one embodiment, the topical carrier may further containsaturated or unsaturated fatty acids such as stearic acid, palmiticacid, oleic acid, palmito-oleic acid, cetyl or oleyl alcohols, stearicacid, fluorinated acids, fluorinated alcohols (e.g.,tetrafluoroethanol), or combinations thereof. The cream may alsooptionally contain one or more surfactants, such as a non-ionicsurfactant.

[0069] In one embodiment, the polyoxometalate topical composition iscomposed of a perfluoropolyether and the counterion A of the POM issilver. In another embodiment, the polyoxometalate topical compositionis composed of a perfluoropolyether and the metal compound is a silvercompound, a gold compound, or a combination thereof. In anotherembodiment, the non-POM material comprises a topical carrier composed ofa perfluoropolyether and the metal compound comprises a silver compound,preferably AgNO₃ or AgClO₄.

[0070] In another embodiment, the non-POM topical composition iscomposed a perfluoropolyether and the metal compound comprises a ceriumcompound, a silver compound, a palladium compound, a platinum compound,or a silver compound.

[0071] A wide variety of powders and coatings known in the art can beused as the material of the present invention. In one embodiment, thepowder comprises activated carbon.

[0072] Any fabric known in the art can be used to produce apolyoxometalate fabric or non-POM fabric of the present invention. Inone embodiment, fabrics used to prepare garments, draperies, carpets,and upholstery can be used and articles made from them are a part ofthis invention In another embodiment, the fabric can be a knit ornon-woven fabric. Useful fibers include, but are not limited to,polyamide, cotton, polyacrylic, polyacrylonitrile, polyester,polyvinylidine, polyolefin, polyurethane, polytetrafluoroethylene, orcarbon cloth, or a combination thereof. In one embodiment, the fabric isprepared from cotton, polyacrylic, or polyacrylontrile. In oneembodiment, the fabric is prepared from a cationic fiber. In anotherembodiment, the fabric comprises (1) a 50/50 blend of nylon-6,6 andcotton or (2) stretchable carbon blended with polyurethane.

[0073] Any cellulosic fiber can be incorporated by a POM or metalcompound to produce the polyoxometalate fibers or non-POM fibers of thepresent invention. Examples of useful cellulosic fibers include, but arenot limited to, wood or paper. In a preferred embodiment, apolyoxometalate or the metal compound of the present invention can beincorporated in paper in order to remove a contaminant from the gas orliquid phase. In one embodiment, the paper is wallpaper.

[0074] The amount of polyoxometalate or metal compound incorporated intothe material varies depending upon the contaminant to be removed and thematerial that is selected. There is no restriction on the amount of POMor metal compound that can be incorporated into the material. In oneembodiment, the amount of polyoxometalate or metal compound incorporatedin the material is from 0.1 to 95% by weight of the polyoxometalatematerial or non-POM material. In one embodiment, the lower limit ofpolyoxometalate or metal compound by weight is 0.1, 0.5, 1.0, 2.0, 5.0,10, 15, 20, 25, 30, 35, 40, 45, or 50%, and the upper limit is 30, 40,50, 60, 70, 80, 90, or 95%. In one embodiment, when the material is atopical carrier, the polyoxometalate or metal compound is from 5 to 30%by weight of topical composition.

[0075] The present invention is capable of removing a single contaminantor multiple contaminants from an environment. The term “environment” asused herein refers to any media that contains at least one contaminant.In one embodiment, the environment comprises a liquid phase. In anotherembodiment, the environment comprises a gas phase.

[0076] The term “remove” refers to, but is not limited to, thedegradation of the contaminant, the conversion of the contaminant intoanother compound that is either less toxic or nontoxic and/ormalodorous, or the adsorption of the contaminant by the polyoxometalateor the metal compound. The POM and metal compound can degrade thecontaminant by a number of different mechanisms For example, the POM canaerobically oxidize the contaminant acetaldehyde (CH₃CHO). Not wishingto be bound by theory, it is believed that the aerobic oxidation ofCH₃CHO proceeds by a radical chain mechanism (i.e., the initiation ofthe radical chain by CH₃CHO+POM_(ox)−>CH₃CO⁻+HPOM_(red)).

[0077] Contaminants that can be removed by using the present inventioninclude, but are not limited to, an aldehyde, an aliphatic nitrogencompound, a sulfur compound, an aliphatic oxygenated compound, ahalogenated compound, an organophosphate compound, a phosphonothioatecompound, a phosphorothioate compound, an arsenic compound, achloroethyl-amine compound, a phosgene compound, a cyanic compound, or acombination thereof. In one embodiment, the contaminant is acetaldehyde,methyl mercaptan, ammonia, hydrogen sulfide, methyl sulfide, diethylsulfide, diethyl disulfide, dimethyl sulfide, dimethyl disulfide,trimethylamine, styrene, propionic acid, n-butyric acid, n-valeric acid,iso-valeric acid, pyridine, formaldehyde, 2-chloroethyl ethyl sulfide,carbon monoxide, or a combination thereof. In another embodiment, thepolyoxometalate materials and non-polyoxometalate materials can removemicrobial life from the gas or liquid phase. Examples of microbial lifeinclude, but are not limited to, bacteria, protozoa, and viruses.

[0078] In another embodiment, the contaminant is a chemical warfareagent (CWA). The chemical warfare agents disclosed in Marrs, Timothy C.;Maynard, Robert. L; Sidell, Frederick R.; Chemical Warfare AgentsToxicology and Treatment; John Wiley & Sons: Chichester, England, 1996;Compton, James A. F. Military Chemical and Biological Agents Chemicaland Toxicological Properties; The Telford Press: Caldwell, N.J., 1988;Somani; Satu M. Chemical Warfare Agents; Academic Press: San Diego,1992, which are herein incorporated by reference in their entirety, canbe removed by the polyoxometalate materials of the present invention.

[0079] The present invention can remove a contaminant from theenvironment in the gas phase under mild conditions. In one embodiment,the contaminant can be removed from −50° C. to 250° C. at a pressure offrom 0.1 ppb to 30 atm, preferably from 25° C. to 105° C. at 1 atm. Inanother embodiment, the lower temperature limit is −50, −40, −30, −20,−10, 0, 10, 20, 50, 75, 100, or 150° C., and the upper temperature limitis 50, 75, 100, 125, 150, 175, 200, 225, or 250° C. In a preferredembodiment, the present invention can remove a contaminant from theenvironment at room temperature (approximately 25° C.) and at 1 atm. Inanother embodiment, the present invention can remove a contaminant fromthe gas phase that has a partial pressure of from 0.1 ppb to 2 atm, 10ppb to 2 atm, 100 ppb to 2 atm, 200 ppb to 2 atm, and 0.5 ppm to 2 atm.Similarly, the present invention can remove a contaminant under mildconditions when the environment is a liquid phase. In one embodiment,the contaminant can be removed from a liquid media at from 0° C. to 200°C. The temperature depends upon the liquid media that is being contactedand the contaminant to be removed.

[0080] The POMs and metal compounds are typically used in the presenceof an oxidizer to remove a contaminant from the environment. In oneembodiment, the POMs and/or metal compounds are used in the presence ofair, which oxidizes the POM and/or metal compound. In anotherembodiment, additional oxidizers can be used in combination with air tooxidize the POM and/or metal compound. Examples of oxidizers include,but are not limited to, peroxides and peracids. In a preferredembodiment, air is used as the oxidizer.

[0081] The environment containing the contaminant can be contacted bythe polyoxometalate materials or non-POM materials using a variety oftechniques. For example, when the contaminant is in the liquid phase,the polyoxometalate material or non-POM material can be dipped orsubmersed into the liquid phase. Alternatively, the liquid phase can befiltered or passed through the polyoxometalate material or non-POMmaterial When the contaminant is in the gas phase, the polyoxometalatematerial or non-POM material is typically placed in an open or closedenvironment that contains the contaminant(s).

[0082] The polyoxometalate materials or non-POM materials of the presentinvention have a number of advantages over the prior art materials thatdo not use a polyoxometalate to remove a contaminant from theenvironment. One advantage is that the present invention can remove acontaminant from the environment starting within milliseconds of contactand can remove the contaminant for extended periods of time, rangingfrom several days to indefinitely. The POMs and metal compounds used inthe present invention are capable of being regenerated to an active formthat permits the removal of the contaminant. Another advantage is thatsome POMs and metal compounds can render the material more waterresistant and increase the surface area of the material. Finally, whenthe material is a fabric or cellulosic fiber, the POM and metal compoundcan enhance the dyeability, light fastness, color fastness, and weavingproperties of the fabric or cellulosic fiber.

[0083] The polyoxometalate and metal compound can be incorporated intothe material using techniques known in the art. In one embodiment, whenthe material is a topical carrier, powder, or coating, thepolyoxometalate or metal compound is directly added to and admixed withthe material. In another embodiment, the material (topical carrier,powder, coating, or fabric) is contacted with a mixture comprising thepolyoxometalate or metal compound and a solvent. The polyoxometalate ormetal compound can be soluble, partially soluble, or insoluble in thesolvent, depending upon the polyoxometalate or metal compound andsolvent selected. In one embodiment, the solvent is water. In anotherembodiment, the solvent can be an organic solvent. Examples of organicsolvents useful in the present invention include, but are not limitedto, acetonitrile, acetone, toluene, carbon dioxide, xylenes,1-methyl-2-pyrrolidinone, dimethyl sulfoxide, or an alcohol, such asmethanol, ethanol, 1-propanol, or 2-propanol.

[0084] In one embodiment, when the material is a fabric or cellulosicfiber, the polyoxometalate or metal compound mixture is from 0.1 to 20%by weight polyoxometalate or metal compound and from 80 to 99.9% byweight water, preferably from 0.3 to 15% by weight polyoxometalate ormetal compound and 85 to 99.7% water. Generally, the fabric orcellulosic fiber is dipped or immersed into the mixture containing thePOM or metal compound for several hours to days at a temperature of from0° C. to 100° C., preferably for 2 hours to 2 days at from 25° C. to 80°C. In another embodiment, the POM or metal compound can be admixed witha resin or adhesive, and the resultant adhesive is applied to thesurface of or admixed with the fabric or cellulosic fiber.

[0085] Typically, once the material has been contacted with the POM ormetal compound mixture, the polyoxometalate material or non-POM materialis dried in order to remove residual solvent. In one embodiment, thepolyoxometalate materials or non-POM material is heated from 0° C. to220° C. at or below atmospheric pressure, preferably from 25° C. to 100°C. In another embodiment, the polyoxometalate material or non-POMmaterial is dried in vacuo (i.e., less than or equal to 10 torr).

[0086] In another embodiment, when the material is a fabric orcellulosic fiber, the POM or metal compound can be incorporated into thefabric or cellulosic fiber by depositing the POM or metal compound onthe surface of an existing fabric or cellulosic fiber, covalentlybonding the POM or metal compound to the fibers of the fabric orcellulosic fiber, impregnating or intimately mixing the POM or metalcompound with the fabric or cellulosic fiber, electrostatically bondingthe POM or metal compound to the fabric or cellulosic fiber, or dativelybonding the POM or metal compound to the fabric or cellulosic fiber viathe coordination of a d- or f-block metal ion on the surface of the POMor metal compound with a functional group on the fabric. In the case ofelectrostatically bonding the POM to the fabric or cellulosic fiber, thepositively charged functional groups on the fabric or cellulosic fiberand the negatively charged POM can form an electrostatic bond. In oneembodiment, when the counterion of the polyoxometalate is a proton orthe metal compound is an acid, the fabric or cellulosic fiber can beprotonated by the polyoxometalate or metal compound to produce apositively charged fiber, which then electrostatically bonds to thepolyoxometalate or metal compound anion. In one embodiment, a cationicpolymer can be used as a binding agent to incorporate an anionicpolyoxometalate or metal compound into an anionic fiber.

EXAMPLES

[0087] The following examples are put forth so as to provide those ofordinary skill in the art with a complete disclosure and description ofhow the compositions, materials, and methods claimed herein are made andevaluated, and are intended to be purely exemplary of the invention andare not intended to limit the scope of what the inventors regard astheir invention. Efforts have been made to ensure accuracy with respectto numbers (e.g., amounts, temperature, etc.) but some errors anddeviations should be accounted for. Unless indicated otherwise, partsare parts by weight, target odorants/toxics are expressed in parts permillion, temperature is in ° C. or is at ambient temperature andpressure is at or near atmospheric.

[0088] The term “consumption” or “consumed” refers to the removal oradsorption of a contaminant or contaminants from the environment or theconversion of the contaminant or contaminants to another compound thatis nontoxic and/or non-malodorous.

[0089] General Considerations

[0090] Materials. PFPE #1511 is composed of 35-50%polytetrafluoroethylene thickening agent dispersed in aperfluoropolyether oil with water as a co-surfactant. PFPE #1511 wasprovided by Dr. E. H. Braue of the United States Army Medical ResearchInstitute for Chemical Defense.

[0091] All reagents used in the examples were obtained from AldrichChemical Company, Milwaukee, Wis., and were used without furtherpurification. The following reagents were used in the examples (thepurity of the reagent is in parenthesis): CEES (98%), HPLC gradeacetonitrile, tetrafluorethylene (99.5%), 1,3-dichlorobenzene (98%),dimethyl sulfoxide (DMSO) (99.8%), AgNO₃ (99+%), HAuCl₄ (99+%), CuCl₂(99+%), FeCl₃ (98%), AgClO₄ (99.9%), (NEt₄)AuCl₂, CuSO₄(99.99%), MnSO₄(98%), VOSO₄ (99.99%), Ti(SO₄)₂ (99%), Fe₂(SO₄)₃(97%), NiSO₄ (99%),ZnSO₄ (99%), Cr₂(SO₄)₃ (99.999%), MgSO₄ (99%), CoSO₄ (99.998%), Pd(NO₃)₄(98%), Na₂SO₃ (99%), and NBu₄NO₃ (97%). NBu₄NO₂ (98%) was purchased fromFluka.

[0092] Synthesis of Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀

[0093] Na₅PV₂Mo₁₀O₄₀ was prepared by the literature procedure outlinedin Petterson, L.; Andersson, I.; Selling, A.; Grate, J. H. Inorg. Chem.1994, 33, 982. Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀ was prepared using the followingprocedure. Ground H₅PV₂Mo₁₀O₄₀ (30.9 g, 1.78×10⁻² mol) was dissolved in200 mL of distilled water. The orange solution was filtered three timesto remove any undissolved POM. Ground AgNO₃ (15.2 g, 8.94×10⁻² mol) wasadded with vigorous stirring. The mixture was stirred overnight at roomtemperature. The product precipitated as a dark red-orange powder andwas removed by suction filtration over a medium fritted glass funnel.The product was dried in vacuo overnight. The IR spectrum of theresultant powder confirmed the formation of Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀.

[0094] Synthesis of Additional Polyoxometalates

[0095] The following POMs listed in Table 8 were prepared by literatureprocedures (the entry number in Table 8 and the bibliographicalinformation are in parenthesis):

[0096] Na₅CuPW₁₁O₃₉; Na₅MnPW₁₁O₃₉; K₅MnPW₁₁O₃₉; and K₅CoPW₁₁O₃₉: Entries2-4 and, 6, respectively; Maksimov, G. M.; Kustoa G. N.; Matveev, K. I.Lazarenko, T. P Koord. Khim. 1989, 15(6), 788-96).

[0097] Na₅PV₂Mo₁₀O₄₀ and H₅PV₂Mo₁₀ ₄₀: (Entries 7 and 20, respectively;O'Donnell, Stephen E.; Pope, Michael T. J. Chem. Soc., Dalton Trans.1976, 21, 2290-7).

[0098] Na₄PVMo₁₁O₄₀: (Entry 11; So, Hyunsoo; Pope, Michael T. Inorg.Chem. 1972, 11(6), 1441-3).

[0099] Na₆PV₃Mo₉O₄₀ and H₆PV₃Mo₉O₄₀: (Entries 8 and 21, respectively;Pope, Michael T.; O'Donnell Stephen E.; Prados, Ronald A. J. Chem. Soc.,Chem. Commun. 1975, 1, 22-3).

[0100] Na₅H₂PV₄Mo₈O₄₀ and H₇PV₄Mo₈O₄₀: (Entries 9 and 22, respectively;Yurchenko, E. N. J. Mol. Struct. 1980, 60, 325-31).

[0101] Na₅FeSiW₁₁O₃₉ and K₆FeSiW₁₁O₃₉: (Entries 12 and 36, respectively;Peacock, R. D.; Weakley, T. J. R. J. Chem. Soc. A 1971, 12, 1937-400).

[0102] Na₅SiVW₁₁O₄₀: (Entry 13; Tourne, Claude; Tourne, Gilbert. Bull.Soc. Chim. Fr. 1969, 4, 1124-36).

[0103] K₈Co(II)P₂W₁₇O₆₁: (Entry 15; Marcu, Gheorghe; Patrut, Adrian;Botar, Alexandru. Rev. Chim. (Bucharest) 1989, 40(11), 870-5).

[0104] K₁₂Pd₃(PW₉O₃₄)₂: (Entry 16; Kuznetsova, N. I.; Kuznetsova, L. I.;Detusheva, L. G.; Likholohov, V. A.; Fedotov, M. A.; Koscheev, S. V.;Burgina, E. B. Stud. Surf. Sci. Catal. 1997, 110 (3rd World Congress onOxidation Catalysis, 1997), 1203-1211).

[0105] K₈Cu(II)P₂W₁₇O₆₁: (Entry 17; Hamlaoui, Mohamed Larbi; Vlasseiko,Konstantin; Messadi, Djelloul. C. R. l'Academie Sci., Ser. II Univers1990, 311(7), 795-8).

[0106] Na₄PVMo₁₁O₄₀ and Na₃PMo₁₂O₄₀: (Entries 18 and 19, respectively;So, Hyunsoo; Pope, Michael T. Inorg. Chem. 1972, 11(6), 1441-3).

[0107] Na₁₆P₄W₃₀Cu₄O₁₁₂: (Entry 24; Huang, Ru-Dan; Bei, Bao-Li; Wang,En-Bo; Li, Bai-Tao; Zhang, Su-Xia Gaodeng Xuexiao Huaxue Xuebao 1998,19(11), 1721-1723).

[0108] K₁₀Ce(PW₁₁O₃₉)₂: (Entry 26; Peacock, R. D.; Weakley, T. J. R. J.Chem. Soc. A 1971, 12, 1937-40).

[0109] K₇CuSiW₁₁O₃₉ and Na₇CuSiW₁₁O₃₉: (Entries 27 and 30, respectively;Teze, Andre; Souchay, Pierre. C. R. Acad. Sci., Ser. C 1973, 276(19),1525-8).

[0110] Na₅NiPW₁₁O₃₉: (Entry 31; Maksimov, G. M.; Kustova, G. N.;Matveev, K. I.; Lazarenko, T. P. Koord. Khim. 1989, 15(6), 788-96).

[0111] Na₃AsW₁₂O₄₀: (Entry 35; Tsyganok, L. P.; Statsenko, V. P.;Vil'dt, A. L. Zh. Neorg. Khim. 1974, 19(11), 3071-7).

[0112] K₈NiP₂W₁₇O₆₁: (Entry 37; Hamlaoui, Mohamed Larbi; Vlassenko,Konstantin; Messadi, Djelloul. C. R. l'Academie Sci., Ser. II Univers1990, 311(7), 795-8).

[0113] (Me₄N)₁₀(Co₃SiW₉O₄₀H₆): (Entry 38; Nomiya, Kenji; Miwa, Makoto.Polyhedron 1985, 4(8), 1407-12).

[0114] Na₃V₁₀O₂₈: (Entry 40; Preuss, F.; Rosenhahn, L. J. Inorg. Nucl.Chem. 1972, 34(5), 1691-703).

[0115] K₈P₂W₁₇(NbO₂)O₆₁: (Entry 42; Gong, Jian, Li, Guoping; Wang,Fuquan; Qu, Lunyu. Wuji Huaxue Xuebao 1995, 11(3), 232-7).

[0116] (NH₄)₆P₂FeW₁₇O₆₁: (Entry 43; Peacock, R. D.; Weakley, T. J. R. J.Chem. Soc. A 1971, Issue 12, 1937-40).

[0117] K₇Mn(II)P₂W₁₇O₆₁: (Entry 44; Marcu, Gheorghe; Patrut, Adrian;Botar, Alexandru. (1). Rev. Chim. (Bucharest) 1989, 40(11), 870-5).

[0118] (NH₄)₆P₂W₁₈O₆₂: (Entry 50; Varga, Gideon M., Jr.;Papaconstantinou, Elias; Pope, Michael T. Inorg. Chem. 1970, 9(3),662-7).

[0119] Na₉PV₆Mo₆O₄₀: (Entry 1; Ret'yakov, V. P.; Volkova, L. K;Zimatseva, G. P.; Rudakov, E. S. Kinet. Katal. 1993, 34(1), 183).

[0120] K₁₂Cu₃(W₉PO₃₄)₂: (Entry 10; Weakley, Timothy J. R.; Finke,Richard G. Inorg. Chem. 1990, 29(6), 1235-41).

[0121] K(NH₄)₆RuBW₁₁O₃₉: (Entry 34; Liu, Huizhang; Sun, Wenliang; Yue,Bin; Li, Mingxing; Chen, Zhijiang; Jin, Songlin; Xie, Gaoyang; Shao,Qianfen; Wu, Tailiu; Chen, Shiming; Yan, Xiaoming. Wuji Huaxue Xuebao1997, 13(3), 251-257).

[0122] K₁₀Ni₄P₂W₁₇O₆₁: (Entry 14; You, David K; Miller, Warren K; Novet,Thomas; Domaille, Peter J.; Evitt, Eric; Johnson, David C.; Finke,Richard G. J. Am. Chem. Soc. 1991, 113(19), 7209-21).

[0123] K₁₀Co₄P₂W₁₈O₆₈: (Entry 39; Evans, Howard T.; Tourne, Claude M.;Tourne, Gilbert F.; Weakley, Timothy J. R. J. Chem. Soc., Dalton Trans.1986, 12, 2699-705).

[0124] K10Mn4(PW₉O₃₄)₂: (Entry 41; Gomez-Garcia, C. J.; Coronado, E.;Gomez-Romero, P.; Casan-Pastor, N. Inorg. Chem. 1993, 32(15), 3378-81).

[0125] K₁₀Cu₄P₂W₁₈O₆₈: Entry 45; Weakley, Timothy J. R.; Finke, RichardG. Inorg. Chem. 1990, 29(6), 1235-41).

[0126] K₁₂P₂W₁₈Ni₃O₆₈: (Entry 47; Gomez-Garcia, Carlos J.; Coronado,Eugenio; Ouahab, Lahcene. Angew. Chem. 1992, 104(5), 660-2).

[0127] Na₆P₄W₃₀Mn(II)₄O₁₁₂: (Entry 49; Gomez-Garcia, C. J.;Borras-Almenar, J. J.; Coronado, E.; Ouahab, L. Inorg. Chem. 1994,33(18), 4016-22).

[0128] K₈Co₂W₁₁O₃₉: (Entry 29; Walmsley, F. J. Chem. Ed. 1992, 69(11),936-38).

[0129] (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆: (Entry 51; Minami, N.; Hiraoka, M.;Izumi, K.; Uchida, Y. Japanese Patent JP 08113731 A2 1996, Chem. Abstr.1996, 125, 117542).

[0130] Na₃H₃PMo₉O₃₄: (Entry 48; Inouye, Y.; Tokutake, Y.; Kunihara, J.;Yoshida, T. Yamase, Y.; Nakata, A.; Nakamura, S. Chem. Pharm. Bull.1992, 40, 805-807).

[0131] K₈CoVW₁₁O₄₀: (Entry 28; Bas-Serra, J.; Todorut, et al. Synth.React. Inorg. Met.-Org. Chem. 1995, 25(6), 869-82).

[0132] H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂]: (Entry 25; Shigeta, S.;Mori, S.; Watanbe, J.; Baba, M.; Khekin, A. M.; Hill, C. L.; Schinazi,R. F. Antiviral Chem. Chemother. 1996, 346-352).

[0133] K₆SiTiW₁₁O₄₀: (Entry 33; Blasecki, J. W. Top. Mol. Org. Eng.1994, 10, 373-385).

[0134] K₈Cu(II)P₂W₁₇O₆₁: (Entry 17; Marcu, Gheorghe; Patrut, Adrian;Botar, Alexandru. Rev. Chim. (Bucharest) 1989, 40(11), 870-5).

[0135] (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂: (Entry 5; Gong, J., Chen, et al.Polyhedron, 1996, 15, 2273-7).

[0136] The following POMs were prepared by the following experimentalprocedures.

[0137] K₅Si(NbO₂)W₁₁O₄₀ (Entry 46): 1.0 g of K₇HNb₆O₁₆ was dissolved in75-mL of deionized H₂O. To this solution, 2-mL of 30% H₂O₂ was added. Afew drops of 3M HCl were added to bring the pH to approximately 6.K₈SiW₁₁O₃₉ (15.8 g) was added, which resulted in gas evolution. To theswirling mixture, 25-mL of H₂O followed by 12-mL of 3M HCl were added.The color of the solution was yellow and the pH was approximately 1. Themixture was stirred for an additional 30 minutes, then 14 g of solid KClwas added, which resulted in the formation of a pale yellow solid. Thesolid was collected by filtration and dried resulting in 4.7 g ofK₅Si(NbO₂)W₁₁O₄₀.

[0138] Na₆SiVNbW₁₁O₃₉ (Entry 32): 6.64 g of K₇Hb₆O₁₉ was dissolved in800-mL of H2O. To this solution, 80-mL of 30% H₂O₂ solution was addedand the pH was adjusted to 6.0 with KOH. Solid K₉SiVW₁₀O₃₉ was addedslowly to produce a final pH of 8.5. To this mixture, 40-mL of 3M HClwas added dropwise. The addition was stopped occasionally to agitate thesolid. The solution was then stirred for 15 minutes. Additional 3M HCl(40-mL) was added to give a pH of 1.5. The solution was stirred for 1hour, and 160 g of solid KCl was added. The orange precipitate wasfiltered off and dried, yielding 40.85 g of K₆SiVNbW₁₁O₃₉. K₆SiVNbW₁₁O₃₉and water were passed through an Amberlite IR-120 ion exchange columnwhich was charged with 1 M NaCl. The volatiles were removed from thecollected solution by vacuum to produce Na₆SiVNbW₁₁O₃₉ as a yellow,crystalline solid. The Amberlite is a product of Rohm and Haas and waspurchased from Aldrich.

[0139] Instrumentation. Gas chromatography analysis was conducted usinga Hewlett-Packard Series 5890 Gas Chromatography equipped with a flameionization detector and fitted with a non-polar 5% PHME siloxane, 30meter column. Alternatively, the gas chromatography was equipped with anFID detector and a 5% phenyl methyl silicone capillary column. Massabundance determinations were performed using a HP 5890 GC with a 5%phenyl methyl silicone capillary column and a 5971A Mass SelectiveDetector. Gas chromatography/mass spectroscopy was performed using aHewlett-Packard Series II 5890 Gas Chromatograph equipped with a 5971Amass selective detector and fitted with a non-polar 5% PHME siloxane, 25meter column. For both GC and GC-MS, nitrogen was used as the carriergas. In Examples 5 and 6, all reactions were monitored using aHewlett-Packard 6890 gas chromatograph with flame ionization detectorand HP-5 (5% phenylmethylsilicone capillary column. UV-visible spectrawere run on a HP 8452A Diode Array Spectrophotometer. The percentages ofO₂ of the reaction atmosphere were varied using a Series 810 Mass Trakflowmeter with dried argon as the other gas.

Example 1 Oxidation of CEES to CEESO by a POM/TSP Mixture under AmbientConditions after 40 Days

[0140] PFPE #1511 (0.525 g) was combined with Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀(0.066 g, 3.81×10⁻⁵ mol) to give a 11% weight/weight POM/cream mixture.The POM/cream mixture was placed in a 18 mL glass vial fitted with apoly(tetrafluoroethylene) (PTFE) stopper. A sufficient amount of2-chloroethyl ethyl sulfide (CEES) was added to the mixture tocompletely submerge the POM/cream mixture. After 40 days, 10 μL of theCEES solution surrounding the POM/cream/mixture was removed and dilutedinto 100 μL of 2,2,2-trifluoroethanol (TFE). GC-MS of this solutionshowed the presence of 2-chloroethyl ethyl sulfoxide (CEESO).

Example 2 Oxidation of CEES to CEESO by POM/TSP Mixtures under AmbientConditions

[0141] The CEES composition used in all trials was composed of 9.0 mL ofCEES combined with 100 μL of 1,3-dichlorobenzene, where the1,3-dichlorobenzene was added as an internal reference. Each POM/PFPE#1511 cream mixture (approximately 0.3 g) was smeared at the bottom ofan 18 mL glass vial and fitted with a PTFE cap. The CEES composition(1.0 mL) was then added and each vial was left undisturbed for severaldays under ambient conditions, with periodic GC analysis of theCEES/reference solution to check for CEESO formation. For GC analysis,10 μL of the CEES/reference solution surrounding the POM/cream mixturewas diluted in 100 μL of TFE and analyzed. The results are shown inTable 1. TABLE 1 Weight Turnovers after Entry Catalyst Percent^(a) 9Days^(b) 1 cream only N/A 0 2 AgNO₃ 20.3% 0 3 H₅PV₂Mo₁₀O₄₀ 5.8% 0 4H₅PV₂Mo₁₀O₄₀ 20.8% 0 5 Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀ 5.6% 0 6Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀ 20.6% 0 7 HAuCl₄ 7.1% 0 8 HAuCl₄, AgNO₃ 7.6% 5AgClO₄ ^(c)

Example 3 Catalytic Oxidation of CEES by POMs in 2,2,2-Trifluoroethanolafter 14 Days under Ambient Conditions

[0142] A CEES solution was prepared by mixing 85.8 mM of CEES; 1.51×10⁻⁵to 1.82×10⁻⁵ mol of catalyst; 100 μL 1,3-dichlorobenzene (internalstandard); and 85 mL of 2,2,2-trifluoroethanol, at 25° C. under ambientair. In a typical run, 5.0 mL of the CEES solution was combined withenough catalyst to yield a CEES:POM ratio of 20:1, and the mixture wasstirred for 14 days. The results are shown in Table 2. TABLE 2 EntryCatalyst CEESO Turnovers^(a) 1 AgNO₃ 0.42 2 Ag_(x)H_(5-x)PV₂Mo₁₀O₄₀ 8.133 Ag_(x)H_(4-x)PVMo₁₁O₄₀ 1.18 4 Na₅PV₂Mo₁₀O₄₀ 0.00 5 K₅CoVW₁₁O₄₀ 0.00 6K₅Cu^(II)PW₁₁O₃₉ 15.33 7 Ag_(x)K_(12-x)Ce(PW₁₁O₃₉)₂ 4.47 8(NH₄)₂Ce(NO₃)₆ 18.53 9 Ag_(x)K_(5-x)Cu^(II)PW₁₁O₃₉ 15.21

Example 4 Aerobic Oxidation of Acetaldehyde Catalyzed byPolyoxometalates

[0143] In a 20 mL vial, 0.961 mmol acetaldehyde, 2 mg of POM, andpentane (internal standard) (34.7 μL) were stirred in 2 mL ofchlorobenzene under 20 mL (0.82 mmol) of O₂ at 298 K for 24 hours. Underthese conditions, the POM was totally insoluble at all times during thereaction. For the cloth samples, the polyoxometalate was deposited as a5% by weight solution of H₂O and subsequently dried. BHT(2,6-di-tert-butyl-p-cresol) was used as a radical inhibitor in a 1.2mol ratio versus POM. The aerobic oxidation of acetaldehyde by the POMsis shown in Table 3. TABLE 3 Time Equivalents % Conversion of % YieldEntry Catalyst (h) CH₃CHO^(a) Acetaldehyde^(b) Acetic Acid^(c)Turnovers^(d) 1 Blank 24 — 8 0 — 2 Na₈Co₂W₁₁O₃₉ 24 1538 97.8 67.2 1033 3K₈SiCoVW₁₀O₃₉ 24 1521 95.7 60.2 916 4 K₇SiCoVW₁₀O₃₉ 24 1483 92.3 55.8827 5 Blank 28.5 — 37 10 — 6 Na₈Co₂W₁₁O₃₉ 28.5 3075 80.3 70.3 1844 7K₈SiCoVW₁₀O₃₉ 28.5 3041 72.1 59.4 1491 7 K₇SiCoVW₁₀O₃₉ 28.5 2966 73.362.4 1545 8 Cotton-Na₈Co₂W₁₁O₃₉ 24 1538 98.2 66.2 815 9Cotton-K₈SiCoVW₁₀O₃₉ 24 1521 90.4 50.0 644 10 1 Na₈Co₂W₁₁O₃₉/1.2 BHT 241538 17.8 22.4 180

Example 5 Aerobic Oxidation of Tetrahydrothiophene in Liquid Phase byModified Polyoxometalates and Metal Compounds

[0144] Tetrahydrothiophene (THT) (0.445 mmol, 0.64 M) and1,3-dichlorobenzene (internal standard) in the presence or absence ofthe polyoxometalate and/or metal compound were stirred in 4 mL ofacetonitrile in 20 mL vials under 1 atm O₂ at room temperature. Theaerobic oxidation of THT by modified polyoxometalates and metalcompounds is shown in Table 4. In Entries 3-7 and 12, 2×10⁻⁶ mol ofpolyoxometalate or metal compound was placed in the vial before addingthe reagent and internal standard. In Entries 8-14, the polyoxometalateand metal compound (Entries 11 and 14) or the metal compounds wereplaced in the vial before the addition of the reagent and the internalstandard. In Entries 8-14, 2×10⁻⁶ mol of each POM or metal compound wasused in a 1/1 ratio. TABLE 4 Entry Catalyst Time (h) Yield %^(a)Turnover^(b) 1 Blank^(c)  3.5 0 — 2 Blank^(c) 72^(d) 0 — 3 H₅PV₂Mo₁₀O₄₀ 3.5 0 0 4 HAuCl₄  3.5 0 0 5 HAuCl₄ 72^(d) 0 0 6 (NH₄)₂Ce(NO₃)₆  3.5 1412 7 (NH₄)₂Ce(NO₃)₆ 72^(d) 26 100 8 (NH₄)₂Ce(NO₃)₆ +  3.5 14 12H₅PV₂Mo₁₀O₄₀ 9 (NH₄)₂Ce(NO₃)₆ +  3.5 67 57 HAuCl₄ 10 (NH₄)₂Ce(NO₃)₆ +72^(d) 76 293 HAuCl₄ 11 (NH₄)₂Ce(NO₃)₆ + HAuCl₄ +  3.5 65 56H₅PV₂Mo₁₀O₄₀ 12 H₂PtCl₆  3 0 0 13 (NH₄)₂Ce(NO₃)₆ +  3 25 21 H₂PtCl₆ 14(NH₄)₂Ce(NO₃)₆ + H₂PtCl₆ +  3 26 23 H₅PV₂Mo₁₀O₄₀

Example 6 Aerobic Oxidation of CEES in Liquid Phase by ModifiedPolyoxometalates and Metal Compounds

[0145] CEES (0.337 mmol, 0.64 M) and 1,3-dichlorobenzene (internalstandard) in the presence or absence of the polyoxometalate and/or metalcompound were stirred in 4 mL of acetonitrile in 20 mL vials under 1 atmof O₂ at room temperature. The aerobic oxidation of CEES by modifiedpolyoxometalates and metal compounds is shown in Table 5. In Entries 2,3, 5, and 6, 2×10⁻⁶ mol of polyoxometalate or metal compound was placedin the vial before adding the reagent. In Entries 4 and 7-12, thepolyoxometalate and/or the metal compound(s) (2×10⁻⁶ mol) were placed inthe vial before adding the reagent solution. TABLE 5 Time ConversionEntry Catalyst (day) %^(a) Yield %^(b) Turnover^(c) 1 Blank^(d) 3 0 0 —2 HAuCl₄ 3 0 0 0 3 H₅PV₂Mo₁₀O₄₀ 3 1 0 0 4 HAuCl₄ + H₅PV₂Mo₁₀O₄₀ 3 12 3 25 (NH₄)₂Ce(NO₃)₆ 1 16 8 5 6 (NH₄)₂Ce(NO₃)₆ 3 26 18 12 7 (NH₄)₂Ce(NO₃)₆ +HAuCl₄ 1 28 9 6 8 (NH₄)₂Ce(NO₃)₆ + HAuCl₄ 3 57 36 24 9 (NH₄)₂Ce(NO₃)₆ +H₅PV₂Mo₁₀O₄₀ 1 47 24 15 10 (NH₄)₂Ce(NO₃)₆ + H₅PV₂Mo₁₀O₄₀ 3 64 41 27 11(NH₄)₂Ce(NO₃)₆ + HAuCl₄ + H₅PV₂Mo₁₀O₄₀ 1 53 43 28 12 (NH₄)₂Ce(NO₃)₆ +HAuCl₄ + H₅PV₂Mo₁₀O₄₀ 3 82 70 46

Example 7 Aerobic Oxidation of CEES in Liquid Phase by a Polyoxometalateand HAuCl₄

[0146] Each POM (9.61×10⁻⁶ mol); HAuCl₄ (4.8×10⁻⁵ mol);1,3-dichlorobenzene (9.61×10⁻⁴ mol), and CEES (9.61×10⁻⁴ mol) werestirred in 4 mL of acetonitrile under 20 mL (0.82 mmol) of O₂ at 298 K.The aerobic oxidation is shown in Table 6. TABLE 6 Time Turnovers^(a)Time Turnovers^(b) Entry Catalyst (h) of CEESO (h) of CEESO 1Na₄PVMo₁₁O₄₀ 4 0 11 1.1 2 Na₅PV₂Mo₁₀O₄₀ 4 5.0 11 10.6 3 Na₆PV₃Mo₉O₄₀ 47.0 11 18.3 4 Na₅H₂PV₄W₈O₄₀ 4 4.4 11 14.2 5 Na₉PV₆Mo₆O₄₀ 4 5.6 11 20.7 6Na₅CuPW₁₁O₃₉ 4 59.2 11 83.6 7 HAuCl₄ 4 0 11 0

Example 8 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO)using AgNO₃/HAuCl₄ System (Non-POM System)

[0147] A metal compound solution was prepared by combining AgNO₃(1.0×10⁻⁵ mol) and HAuCl₄ (5.0×10⁻⁶ mol) in 1 mL of acetonitrile. Tothis solution was added CEES (3.0×10⁻³ mol). Upon addition of CEES tothe solution, a white precipitate immediately formed. The precipitate isbelieved to be a silver containing salt, possibly coordinated to CEES.The solution was allowed to stir for 100 hours, at which time there wasloss of CEES in the solution based on gas chromatography. The filtratewas taken to dryness, and a solution containing excess CEES inacetonitrile was added to the yellow oily residue. Gas chromatography ofthe solution confirmed the formation of CEESO. The results are shown inTable 7 (entries 1-7).

Example 9 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO)using AgNO₃/AgClO₄/HAuCl₄ System (Non-POM System)

[0148] A 20 mL vial fitted with a PTFE septum was purged with 1 atm ofO₂. To this vial were added by syringe, 0.035 mL of AgNO₃ (0.1013 M inacetonitrile); 0.060 mL of AgClO₄ (0.1138 M in acetonitrile); and 0.100mL HAuCl₄ (0.0477 M in acetonitrile), and the total volume was adjustedto 1 mL with the addition of HPLC grade acetonitrile. To this solution,0.36 mL (2.86×10⁻³ mol) of CEES were added to the solution, and theformation of CEESO was monitored over time by gas chromatography using1,3-dichlorobenzene as the internal reference. The results aresummarized in Table 7 (Entries 8-11). TABLE 7 Entry Catalyst Time (hrs)Turnover^(a) 1 2AgNO₃ 100 0 2 2AgClO₄ 100 0 3 1HAuCl₄ 100 0.9 4 2AgNO₃ +1HAuCl₄ 1 13.0 5 2AgNO₃ + 1HAuCl₄ 2 21.3 6 2AgNO₃ + 1HAuCl₄ 24 83.5 72AgNO₃ + 1HAuCl₄ 100 146.3 8 0.75AgNO₃ + 1.25AgCl₄ + 1HAuCl₄ 1 38.3 90.75AgNO₃ + 1.25AgCl₄ + 1HAuCl₄ 2 50.2 10 0.75AgNO₃ + 1.25AgCl₄ +1HAuCl₄ 24 141.9 11 0.75AgNO₃ + 1.25AgCl₄ + 1HAuCl₄ 100 208.7

Example 10 Aerobic Oxidation of CEES by POM/HAuCl₄ and MetalCompound/HAuCl₄ Systems

[0149] One equivalent of the POM or metal compound was combined withfive equivalents of HAuCl₄ in acetonitrile, wherein the total volume was1 mL. To this solution, 100 equivalents of CEES was added. The reactionwas conducted under one atm of O₂ at 298 K. The number of turnovers werecalculated at 4 and 11 hours, and the results are summarized in Table8a. TABLE 8a Turn- Entry POM or Metal Compound Turnovers^(a) overs^(b) 1Na₉PV₆Mo₆O₄₀ 5.6 20.7 2 Na₅CuPW₁₁O₃₉ 59.2 83.6 3 Na₅MnPW₁₁O₃₉ 6.5 29.0 4K₅CoPW₁₁O₃₉ 38.9 71.9 5 (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂ 5.1 27.9 6 K₅PMnW₁₁O₃₉51.8 76.5 7 Na₅PV₂Mo₁₀O₄₀ 5.0 10.6 8 Na₆PV₃Mo₉O₄₀ 7.0 18.3 9Na₅H₂PV₄Mo₈O₄₀ 4.4 14.2 10 K₁₂Cu₃(W₉PO₃₄)₂ 5.1 12.2 11 Na₄PVW₁₁O₃₉ 1.68.7 12 Na₅FeSiW₁₁O₄₀ 0.9 4.6 13 Na₅SiVW₁₁O₄₀ 0.0 2.3 14 K₁₀Ni₄P₂W₁₇O₆₁3.5 7.5 15 K₈Co(II)P₂W₁₇O₆₁ 1.0 2.5 16 K₁₂Pd₃(PW₉O₃₄)₂ 4.2 6.4 17K₈Cu(II)P₂W₁₇O₆₁ 2.0 4.7 18 Na₄PVMo₁₁O₄₀ 0.0 1.2 19 Na₃PMo₁₂O₄₀ 0.0 0.120 H₅PV₂W₁₀O₄₀ 0.0 1.4 21 H₆PV₃W₉O₄₀ 0.0 1.2 22 H₇PV4W₈O₄₀ 0.0 0.9 23HAuCl₄ 0.0 0.0 24 Na₁₆P₄W₃₀Cu₄O₁₁₂ 1.5 1.5 25H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂] 1.0 1.6 26 K₁₀Ce(PW₁₁O₃₉)₂ 0.6 0.727 K₇CuSiW₁₁O₃₉ 1.0 1.1 28 K₈CoVW₁₁O₄₀ 1.3 1.1 29 K₈Co₂W₁₁O₃₉ 1.5 1.0 30Na₇CuSiW₁₁O₃₉ 1.1 1.1 31 Na₅NiPW₁₁O₃₉ 0.6 0.9 32 Na₆SiVNbW₁₁O₃₉ 0.7 0.633 K₆SiTiW₁₁O₄₀ 0.6 0.4 34 K(NH₄)₆RuBW₁₁O₃₉ 0.7 0.9 35 Na₃AsW₁₂O₄₀ 0.70.2 36 K₆FeSiW₁₁O₃₉ 0.9 0.7 37 K₈NiP₂W₁₇O₆₁ 0.9 0.9 38(Me₄N)₁₀(Co₃SiW₉O₄₀H₆) 1.8 1.9 39 K₁₀Co₄P₂W₁₈O₆₈ 1.3 1.6 40 Na₃V₁₀O₂₈1.8 1.7 41 K₁₀Mn₄(PW₉O₃₄)₂ 1.3 1.4 42 K₈P₂W₁₇(NbO₂) 1.1 0.9 43(NH₄)₆P₂FeW₁₇O₆₁ 0.6 0.5 44 K₇Mn(II)P₂W₁₇O₆₁ 1.0 0.8 45 K₁₀P₂W₁₈Cu₄O₆₈1.2 1.9 46 K₅Si(NbO₂)W₁₁O₄₀ 0.9 0.7 47 K₁₂P₂W₁₈Ni₃O₆₈ 1.0 1.8 48Na₃H₃Mo₉O₃₄ 0.8 0.9 49 Na₆P₄W₃₀Mn(II)₄O₁₁₂ 1.1 1.4 50 (NH₄)₆P₂W₁₈O₆₂ 0.00.3 51 (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆ 0.5 1.8 52 CuCl₂ 0.0 0.4 53 FeCl₃ 0.3 0.5

[0150] Additional POM and/or metal compounds that were tested can befound in Table 8b. TABLE 8b Entry Compound A Compound B 1 5 HAuCl₄ 2Na₄PVMo₁₁O₄₀ 3 Na₄PVMo₁₁O₄₀ 5 HAuCl₄ 4 Na₅PV₂Mo₁₀O₄₀ 5 Na₅PV₂Mo₁₀O₄₀ 5HAuCl₄ 6 Na₆PV₃Mo₉O₄₀ 7 Na₆PV₃Mo₉O₄₀ 5 HAuCl₄ 8 Na₅H₂PV₄Mo₈O₄₀ 9Na₅H₂PV₄Mo₈O₄₀ 5 HAuCl₄ 10 Na₉PV₆Mo₆O₄₀ 11 Na₉PV₆Mo₆O₄₀ 5 HAuCl₄ 12Na₄PVW₁₁O₄₀ 13 Na₄PVW₁₁O₄₀ 5 HAuCl₄ 14 Na₃PMo₁₂O₄₀ 15 Na₃PMo₁₂O₄₀ 5HAuCl₄ 16 Na₅CuPW₁₁O₃₉ 5 HAuCl₄ 17 (TBA)₅CuPW₁₁O₃₉ 5 HAuCl₄ 18Na₅MnPW₁₁O₃₉ 19 Na₅MnPW₁₁O₃₉ 5 HAuCl₄ 20 Na₅FeSiW₁₁O₃₉ 21 Na₅FeSiW₁₁O₃₉22 Na₅SiVW₁₁O₄₀ 23 Na₅SiVW₁₁O₄₀ 5 HAuCl₄ 24 Na₅PV₂W₁₀O₄₀ 25 Na₅PV₂W₁₀O₄₀5 HAuCl₄ 26 Na₆PV₃W₉O₄₀ 27 Na₆PV₃W₉O₄₀ 5 HAuCl₄ 28 Na₇PV₄W₈O₄₀ 29Na₇PV₄W₈O₄₀ 5 HAuCl₄ 30 Na₁₆P₄W₃₀Cu₄O₁₁₂ 31 Na₁₆P₄W₃₀Cu₄O₁₁₂ 5 HAuCl₄ 32H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂ 33 H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅6)₂5 HAuCl₄ 34 K₁₀Ce(PW₁₁O₃₉)₂ 35 K₁₀Ce(PW₁₁O₃₉)₂ 5 HAuCl₄ 36 K₇CuSiW₁₁O₃₉37 K₇CuSiW₁₁O₃₉ 5 HAuCl₄ 38 K₈CoVW₁₁O₃₉ 39 K₈CoVW₁₁O₃₉ 5 HAuCl₄ 40K₅CoPW₁₁O₃₉ 41 K₅CoPW₁₁O₃₉ 5 HAuCl₄ 42 K₈Co₂W₁₁O₃₉ 43 K₈Co₂W₁₁O₃₉ 5HAuCl₄ 44 (NDec₄)₆HMnNb₃P₂W₁₅O₆₂ 45 (NDec₄)₆HMnNb₃P₂W₁₅O₆₂ 5 HAuCl₄ 46Na₇CuSiW₁₁O₃₉ 47 Na₇CuSiW₁₁O₃₉ 5 HAuCl₄ 48 Na₅NiPW₁₁O₃₉ 49 Na₅NiPW₁₁O₃₉5 HAuCl₄ 50 Na₆SiVNbW₁₁O₃₉ 51 Na₆SiVNbW11O₃₉ 5 HAuCl₄ 52 K₅PMnW₁₁O₃₉ 53K₅PMnW₁₁O₃₉ 5 HAuCl₄ 54 K₆SiTiW₁₁O₄₀ 55 K₆SiTiW₁₁O₄₀ 5 HAuCl₄ 56K(NH₄)₆RuBW₁₁O₃₉ 57 K(NH₄)₆RuBW₁₁O₃₉ 5 HAuCl₄ 58 Na₃AsW₁₂O₄₀ 59Na₃AsW₁₂O₄₀ 5 HAuCl₄ 60 K₆FeSiW₁₁O₃₉ 61 K₆FeSiW₁₁O₃₉ 5 HAuCl₄ 62K₈NiP₂W₁₇O₆₁ 63 K₈NiP₂W₁₇O₆₁ 5 HAuCl₄ 64 (Me₄N)₁₀(Co₃SiW₉O₄₀H₆) 65(Me₄N)₁₀(Co₃SiW₉O₄₀H₆) 5 HAuCl₄ 66 K₁₀Co₄P₂W₁₈O₆₈ 67 K₁₀Co₄P₂W₁₈O₆₈ 5HAuCl₄ 68 Na₃V₁₀O₂₈ 69 Na₃V₁₀O₂₈ 5 HAuCl₄ 70 K₁₀(MN₄)(PW₉O₃₄)₂ 71K₁₀(MN₄)(PW₉O₃₄)₂ 5 HAuCl₄ 72 K₁₂Cu₃(W₉PO₃₄)₂ 73 K₁₂Cu₃(W₉PO₃₄)₂ 5HAuCl₄ 74 K₁₀Ni₄P₂W₁₇O₆₁ 75 K₁₀Ni₄P₂W₁₇O₆₁ 5 HAuCl₄ 76 K₈P₂W₁₇(NbO₂) 77K₈P₂W₁₇(NbO₂) 5 HAuCl₄ 78 (NH₄)₆P₂FeW₁₇O₆₁ 79 (NH₄)₆P₂FeW₁₇O₆₁ 5 HAuCl₄80 K₈Co(II)P₂W₁₇O₆₁ 81 K₈Co(II)P₂W₁₇O₆₁ 5 HAuCl₄ 82 K₁₂Pd₃(PW₉O₃₄)₂ 83K₁₂Pd₃(PW₉O₃₄)₂ 5 HAuCl₄ 84 K₇Mn(II)P₂W₁₇O₆₁ 5 HAuCl₄ 85 K₁₀P₂W₁₈Cu₄O₆₈5 HAuCl₄ 86 K₈Cu(II)P₂W₁₇O₆₁ 5 HAuCl₄ 87 K₅Si(NbO₂)W₁₁O₄₀ 5 HAuCl₄ 88K₁₂P₂W₁₈Ni₃O₆₈ 5 HAuCl₄ 89 Na₃H₆Mo₉O₃₄ 5 HAuCl₄ 90 Na₆P₄W₃₀Mn(II)₄O₁₁₂ 5HAuCl₄ 91 (NH₄)₆P₂W₁₈O₆₂ + 5HAuCl₄ 5 HAuCl₄ 92 (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆ 5HAuCl₄ 93 5 Cu(acetate)₂ 94 Na₅PV₂Mo₁₀O₄₀ 5 Cu(acetate)₂ 95 5 Co(II)Acac96 Na₅PV₂Mo₁₀O₄₀ 5 Co(II)Acac 97 5 Fe(III)Acac 98 Na₅PV₂Mo₁₀O₄₀ 5Fe(III)Acac 99 5 MnO₂ 100 Na₅PV₂Mo₁₀O₄₀ 5 MnO₂ 101 5 CuCl₂ 102Na₅PV₂Mo₁₀O₄₀ 5 CuCl₂ 103 5 FeCl₃ 104 Na₅PV₂Mo₁₀O₄₀ 5 FeCl₃ 105 5 CrCl₃106 Na₅PV₂Mo₁₀O₄₀ 5 CrCl₃ 107 5 CeCl₃ 108 Na₅PV₂Mo₁₀O₄₀ 5 CeCl₃ 109Na₉PV₆Mo₆O₄₀ 5 FeCl₃ 110 Na₉PV₆Mo₆O₄₀ 5 CuCl₂ 111 Na₉PV₆Mo₆O₄₀ 112K₁₂Pd₃(PW₉O₃₆)₂ 5 FeCl₃ 113 K₁₂Pd₃(PW₉O₃₆)₂ 5 CuCl₂ 114 K₁₂Pd₃(PW₉O₃₆)₂115 Na₅CuPW₁₁O₃₉ 116 Na₅CuPW₁₁O₃₉ 5 Cr(NO₃)₃ 117 5 CrNO₃ 118Na₅CuPW₁₁O₃₉ 5 Co(NO₃)₂ 119 5 Co(NO₃)₂ 120 5 Zn(NO₃)₂ 121 Na₅CuPW₁₁O₃₉ 5Zn(NO₃)₂ 122 Na₅CuPW₁₁O₃₉ 5 Cu(NO₃)₂ 123 5 Cu(NO₃)₂ 124 Na₅CuPW₁₁O₃₉ 5Zn(NO3)3 125 Na₅CuW₁₁O₃₉ 5 Cu(acetate)₂ 126 Na₅CuW₁₁O₃₉ 5 Fe(acetate)₂127 Na₅CuW11O₃₉ 5 MnO₂ 128 5 NaNO₃ 129 Li₅PVW₁₁O₄₀ 5 HAuCl₄ 130 AgNO₃131 AgNO₃ 5 HAuCl₄ 132 NaNO₃ 5 HAuCl₄ 133 NaClO₄ 5 HAuCl₄ 134 AgClO₄ 5HAuCl₄ 135 LiClO₄ 5 HAuCl₄ 136 5 (NH₄)₂Ce(NO₃)₆ 137 Na₅PVMo₁₁O₄₀ 5(NH₄)₂Ce(NO₃)₆ 138 Na₅CuPW₁₁O₃₉ 5 (NH₄)₂Ce(NO₃)₆ 139 Na₅PVMo₁₁O₄₀ 5CoSO₄ 140 Na₅CuPW₁₁O₃₉ 5 CoSO₄ 141 Na₅PVMo₁₁O₄₀ 5 Ce(SO₄)₂ 142Na₅CuPW₁₁O₃₉ 5 Ce(SO₄)₂ 143 Na₅PVMo₁₁O₄₀ 5 H₂PtCl₆ 144 Na₅CuPW11O₃₉ 5H₂PtCl₆ 145 Na₅PVMo₁₁O₄₀ 5 Pd(NO₃)₂ 146 Na₅CuPW₁₁O₃₉ 5 Pd(NO₃)₂ 147Na₅PVMo₁₁O₄₀ 5 RhCl₃ 148 Na₅CuPW₁₁O₃₉ 5 RhCl₃ 149 Na₅PVMo₁₁O₄₀ 5 ReO₂150 Na₅CuPW₁₁O₃₉ 5 ReO₂

Example 11 Oxidation of CEES to CEESO by Metal Compounds (Non-POM)

[0151] (a) Determining the Stoichiometry of O, in the CatalyticOxidation of CEES. A Schlenk flask fitted with septum was attached to amanometer and purged with O₂. To the flask containing 1.36 mL ofacetonitrile, solutions (all in acetonitrile) of 0.200 mL of (NEt₄)AuCl₂(5.0×10⁻⁶ mol), 0.188 mL of AgClO₄ solution (1.0×10⁻⁵ mol), 0.094 mLNBu₄NO₃ solution (5.0×10⁻⁶ mol), 0.166 mL 1,3-dichlorobenzene (7.5×10⁻⁴mol) (internal standard for GC), and 0.084 mL CEES (3.8×10⁻⁴ mol) wereadded. The consumption of O₂ was recorded, and aliquots wereperiodically taken and injected into the GC. The stoichiometry of O₂consumption was established using a manometer to determine the amount ofO₂ consumed while simultaneously monitoring CEESO formation with a gaschromatograph FIG. 1 reveals that one equivalent of the CEESO formedcorresponds to 0.5 equivalents of O₂.

[0152] (b) Cream Formulation Reactions. Experiments were performed usingthe perfluorinated oil, Galden DO2, and Fomblin perfluorinated polyetheroil as “solvent,” both of which are components of the cream. Sampleswere prepared by adding components together, dissolving in a minimalamount of acetonitrile, stirring for 10 minutes, and then removing thesolvent by vacuum.

[0153] In all the cases where (NEt₄)AuCl₂ was used as the gold compound,1.25×10⁻⁵ mol of the gold compound was used. The other components whichwere varied in quantities were NBu₄NO₃ (1.25×10⁻⁵−1.25×10⁻⁴ mol), and aCuSO₄ (125×10⁻⁵−1.25×10⁻⁴ mol) (Table 9). The gold, copper, and/ornitrate salts were admixed in acetonitrile, then the solvent was removedby vacuum. After the mixture was dried by vacuum in a Schlenk flask, theflask is attached to the manometer and the apparatus is purged with O₂.After purging, 7.0 mL of the perfluorinated fluid was added to theflask. The system was equilibrated to atmospheric pressure then sealedfrom any external atmosphere. Through the septum 0.05 mL (4.2×10⁻⁴ mol)of CEES was added and the system was monitored for O₂ consumption. Table9 shows CEESO formation after 1 hour using various cream formulations(7.0 mL Galden DO2). TABLE 9^(a) [Au] [NO₃] [Cu⁺²] [CEESO formed] 0 1.251.25 3.62 1.25 1.25 1.25 5.80 0 2.50 2.50 5.00 1.25 2.50 2.50 8.06 05.00 7.25 8.06 1.25 5.00 7.25 16.20 0 10.00 12.50 10.60 1.25 10.00 12.5018.70

[0154] Another experiment was performed using Fomblin as the “solvent.”In this case, 1.0 mL of Fomblin, 0.005 g of (NEt₄)AuCl₂ (1.25×10⁻⁵ mol),was admixed in with varying amounts of CuSO₄, MnSO₄, VOSO₄, Ti(SO₄)₂,Fe₂(SO₄)₃, NiSO₄, ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄, Pd(NO₃)₄, Na₂SO₃,and/or NBu₄NO₃. The catalyst was prepared and the experiment wasperformed using the same method as earlier reported. Table 10 revealsCEESO formation in PFPE Surfactant (1.0 mL Fomblin) using various metalcompounds. The metal compounds are abbreviated for simplicity sake. Forexample, metal compound 1Au/1Cu(II)/1NO₃ was prepared by mixing oneequivalent each of (NEt₄)AuCl₂, CuSO₄, and NBu₄NO₃. TABLE 10 Turnoversof CEESO after 10 min Metal Compound (based on Au) 1Au/1Cu(II)/1NO₃ 171Au/2Cu(II)/1NO₃ 28 1Au/1Cu(II)/2NO₃ 115 1Au/2Cu(II)/2NO₃ 1551Au/1Cu(II)/3NO₃ 155 1Au/1Fe(III)/3NO₃ 142 1Au/2Mn(II)/3NO₃ 1641Au/2Ti(IV)/3NO₃ 142 1Au/2Co(II)/3NO₃ 177 1Au/4NO₃ 185 1Au/2Cu(II)/3NO₃181 1Au/2Cu(II)/4NO₃ 195 1Au/3Cu(II)/3NO₃ 165 2Cu(II)/3NO₃ 28 1Au/3NO₃150 1Fe(III)/3NO₃ 19 1Au/2V(IV)/3NO₃ 160 1Au/2Ni(II)/3NO₃ 1401Au/2Ag(II)/3NO₃ 184

[0155]FIG. 2 shows CEESO formation as a function of time for1Au/2Cu(II)/3NO₃, 2Cu(II)/3NO₃, and 1Au/3NO₃. From the data in Table 10and FIG. 2, it is clear that there was a synergistic effect when certainredox active metals were added to the Au/NO₃ system. For example, one ofthe most active systems, 1Au/2Cu(II)/3NO₃ was 3.8 and 6.5 times moreeffective after 10 minutes of reaction time than when only 2 of thecomponents were used, 1Au/3NO₃ and 2Cu(II)/3NO₃ respectively. Also, FIG.2 shows that inhibition was less pronounced in the three componentsystem. Another important aspect of this system is that the oxidationterminates to the sulfoxide without continued oxidation to yield thesulfone. This is important as it relates to toxicity issues as it isbelieved that the sulfoxide of mustard gas is significantly less toxicthan the corresponding sulfone.

Example 12 Synthesis, Characterization, and Reactivity ofOrgano-Modified POMs

[0156] (a) Synthesis of Ag₂[V₆O₁₃((OCH₂)₃CCH₃)₂] (Ag Me Cap)

[0157] Na₂[V₆O₁₃((OCH₂)₃CCH₃)₂] (Na Me cap, 0.480 g) was dissolved in ˜4mL of distilled water. This was filtered over a medium fritted funnel toremove any undissolved POM. To the dark red-orange solution was addedAgNO₃ (0.215 g) with stirring. An orange-red precipitate formedimmediately. The crude product was separated by suction filtration overa medium frit, washed with room temperature water and ether. The productwas dried over night in vacuo. Crystals were grown by diffusing etherinto an acetonitrile solution of the crude product at room temperature.⁵¹V NMR (0.04 g dissolved in 2.0 mL of MeCN) −499.232 ppm (singlet).Solid-state IR (KBr pellet, 1400-400 cm⁻¹) 1452.11 (m), 1390.47 (w),1200.43 (w), 1128.53 (m), 1015.5 (s), 953.9 (vs), 820.36 (sh), 794.68(s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).

[0158] (b) Synthesis of Co[V₆O₁₃((OCH₂)₃CCH₃)₂] (Co Me Cap)

[0159] The same procedure for the synthesis of Ag₂[V₆O₃((OCH₂)₃CCH₃)₂]was followed, except CoCl₂ was added to form the Co salt of the POM.Crystals were grown from diffusing isopropyl alcohol into a MeCNsolution of crude product. ⁵¹V NMR (0.04 g dissolved in 2.0 mL of MeCN)−500.3 ppm (singlet). Solid-state IR (KBr pellet, 1400-400 cm⁻¹) 1452.11(m), 1390.47 (w), 1200.43 (w), 1128.53 (m), 1015.5 (s), 953.9 (vs),820.36 (sh), 794.68 (s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).

[0160] (c) Reactivity of Organo-Modified POMs

[0161] Table 11 lists the oxidation of tetrahydrothiophene (THT) byt-butylhydroperoxide (TBHP) catalyzed by the transition metal salts ofMe-capped V₆O₁₃. The oxidations were performed by dissolving theparticular salt in acetonitrile to give lightly colored orange-yellowsolutions. The solutions were placed in 24-mL vials fitted with PTFEsepta. THT and TBHP were then syringed in and the reactions weremonitored by quantitative GC. Reactions were stirred at roomtemperature. TABLE 11 Room Temperature Oxidation of THT to THTO by TBHPCatalyzed by Transition Metal Salts of Me Capped V₆O₁₃ after 48 Hours.Mols of Mols of Turnover Catalyst catalyst, ×10⁻⁶ THTO, ×10⁻⁵ number^(b)Na Me cap 1.76 6.03 34.3 Ag Me cap 1.87 5.59 30.0 Co Me cap 1.61 6.3339.3 AgNO₃ 14.1 1.06 0.754 CoCl₂ 39.5 2.25 0.570 blank^(a) NA 0 0

[0162] Throughout this application, various publications are referenced.The disclosures of these publications in their entireties are herebyincorporated by reference into this application in order to more fullydescribe the state of the art to which this invention pertains.

[0163] It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present inventionwithout departing from the scope or spirit of the invention. Otherembodiments of the invention will be apparent to those skilled in theart from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only.

What is claimed:
 1. A polyoxometalate topical composition for removing acontaminant from an environment, comprising a topical carrier and atleast one polyoxometalate, with the proviso that the polyoxometalate isnot H₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; orK₅Co^(III)W₁₂O₄₀.
 2. The composition of claim 1, wherein thepolyoxometalate has the formula 1 of[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A], wherein M is atleast one f-block element or d-block element having at least oned-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, ortantalum; X is at least one p-, d-, or f-block element, wherein X is notoxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o isfrom 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; sis sufficiently large that y is greater than zero; and y is greater thanzero, wherein the sum of k, m, n, o, and p is greater than or equal tofour; and the sum of k, m, and q is greater than zero, and A is one ormore different counterions.
 3. The composition of claim 2, wherein Mcomprises a d-block element having at least one d-electron or a f-blockelement having at least one f-electron.
 4. The composition of claim 2,wherein M comprises titanium, chromium, manganese, cobalt, iron, nickel,copper, rhodium, silver, palladium, platinum, mercury, or ruthenium. 5.The composition of claim 2, wherein M comprises manganese.
 6. Thecomposition of claim 2, wherein M comprises cobalt.
 7. The compositionof claim 2, wherein M comprises ruthenium.
 8. The composition of claim2, wherein M comprises copper.
 9. The composition of claim 2, wherein Xcomprises phosphorus, silicon, aluminum, boron, cobalt, zinc, or iron.10. The composition of claim 2, wherein A comprises a quaternaryammonium cation; proton; alkali metal cation; alkaline earth metalcation; ammonium cation; d- or f-block metal complex, or a combinationthereof.
 11. The composition of claim 2, wherein A comprises cerium,silver, gold, platinum, or a combination thereof.
 12. The composition ofclaim 2, wherein A comprises hydrogen, lithium, sodium, potassium or acombination thereof.
 13. The composition of claim 2, wherein A comprises(1) hydrogen, lithium, sodium, potassium or a combination thereof, and(2) cerium, silver, gold, platinum, or a combination thereof.
 14. Thecomposition of claim 2, wherein A is silver.
 15. The composition ofclaim 2, wherein A is gold.
 16. The composition of claim 2, wherein A isplatinum.
 17. The composition of claim 2, wherein A is cerium.
 18. Thecomposition of claim 2, wherein A is cerium and silver.
 19. Thecomposition of claim 2, wherein A is cerium and platinum.
 20. Thecomposition of claim 2, wherein A is cerium and gold.
 21. Thecomposition of claim 2, wherein A is silver and gold.
 22. Thecomposition of claim 2, wherein A is not hydrogen or potassium.
 23. Thecomposition of claim 2, wherein s is from 19 to
 460. 24. The compositionof claim 2, wherein the sum of k and q is greater than or equal to one,the sum of k, m, n, o, p and q is 12, and s is
 40. 25. The compositionof claim 2, wherein k is not zero.
 26. The composition of claim 2,wherein q is not zero.
 27. The composition of claim 1, wherein thepolyoxometalate has the formula [X^(g+)V_(b) ^(j+)M_(c) ^(h+)Z_(12−b−c)^(i+)O_(x)]^(u−)[A], wherein X is at least one p-, d-, or f-blockelement; g is greater than or equal to 2; M is at least one f-blockelement or d-block element having at least one: d-electron, wherein M isnot vanadium; h is from 1 to 7; i is from 5 to 6; j is from 4 to 5; x is39 or 40; Z is tungsten, molybdenum, niobium, or a combination thereof;b is from 0 to 6; c is from 0 to 6; u is from 3 to 9; and A is acounterion.
 28. The composition of claim 27, wherein the polyoxometalatehas the formula [X^(g+)V_(b) ^(j+)Z_(12−b) ^(i+)O₄₀]^(u−)[A] wherein Xis at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, oriron; b is from 1 to 6, and u is from 3 to
 9. 29. The composition ofclaim 27, wherein the polyoxometalate has the structure [X^(g+)M_(c)^(h+)Z_(12−c) ^(i+)O₄₀]^(u−)[A], wherein X is at least one phosphorus,silicon, aluminum, boron, zinc, cobalt, or iron; c is from 1 to 6, and uis from 3 to
 9. 30. The composition of claim 1, wherein thepolyoxometalate has the formula [X₂ ^(r+)V_(u) ^(s+)M_(v)^(t+)Z_(18−u−v) ^(y+)O_(z)]^(w−)[A], wherein X is at least one p-, d-,or f-block element, r is greater than or equal to 1; M is at least onef-block element or d-block element having at least one d-electron,wherein M is not vanadium; t is from 1 to 7; s is from 4 to 5; Z istungsten, molybdenum, niobium or a combination thereof; u is from 0 to9; v is from 0 to 9; y is from 5 to 6; z is 61 or 62; w is greater thanor equal to 4; and A is a counterion.
 31. The composition of claim 30,wherein the polyoxometalate has the formula [X₂ ^(r+)V_(u) ^(s+)Z_(18−u)^(y+)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur,silicon, aluminum, boron, zinc, cobalt, or iron; u is from 1 to 9; and wis greater than or equal to
 4. 32. The composition of claim 30, whereinthe polyoxometalate has the formula [X₂ ^(r+)M_(v) ^(t+)Z_(18−v)^(y+)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur,silicon, aluminum, boron, zinc, cobalt, or iron; v is from 1 to 9; and wis greater than or equal to
 4. 33. The composition of claim 1, whereinthe polyoxometalate has the formula [YV_(p)Z_(12−p)O₄₀][A], wherein Y isphosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p is from1 to 6, and A is a counterion.
 34. The composition of claim 1, whereinthe polyoxometalate further comprises organic group, an organosilylgroup, an other p-block organometallic group, or a d-blockorganometallic group, wherein the organic group, the organosilyl group,the other p-block organometallic group, or the d-block organometallicgroup is bonded to the polyoxometalate.
 35. The composition of claim 1,wherein the polyoxometalate comprises K₈Co₂W₁₁O₃₉; K₈SiCoVW₁₀O₃₉;K₇SiCoVW₁₀O₃₉; Na₈Co₂W₁₁O₃₉; Ag₅PV₂Mo₁₀O₄₀; Ag₆PV₃Mo₉O₄₀; Ag₈CoVW₁₁O₄₀;Ag₁₂Ce(PW₁₁O₃₉)₂; Na₁₂Ce(PW₁₁O₃₉)₂; K₁₂Ce(PW₁₁O₃₉)₂; Na₅PCuW₁₁O₃₉;H₆PV₃Mo₉O₄₀; or K₅Cu^(II)PW₁₁O₃₉.
 36. The composition of claim 1,wherein the polyoxometalate comprises a modified polyoxometalate,wherein the modified polyoxometalate comprises the admixture of (1) apre-modified polyoxometalate and (2) a cerium compound, a silvercompound, a gold compound, a platinum compound, a copper compound, acobalt compound, or a combination thereof.
 37. The composition of claim36, wherein (1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀ and (2)the cerium compound is (NH₄)₂Ce(NO₃)₆.
 38. The composition of claim 36,wherein (1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀; (2) thecerium compound is (NH₄)₂Ce(NO₃)₆; and (3) the gold compound is HAuCl₄.39. The composition of claim 36, wherein (1) the pre-modifiedpolyoxometalate is H₅PV₂Mo₁₀O₄₀; (2) the cerium compound is(NH₄)₂Ce(NO₃)₆; and (3) the platinum compound is H₂PtCl₆.
 40. Thecomposition of claim 36, wherein (1) the pre-modified polyoxometalate isNa₅PV₂Mo₁₀O₄₀ and (2) the silver compound is AgNO₃, AgClO₄, or acombination thereof.
 41. The composition of claim 36, wherein (1) thepre-modified polyoxometalate comprises Na₄PVMo₁₁O₄₀; Na₅PV₂Mo₁₀O₄₀;Na₆PV₃Mo₉O₄₀; Na₅H₂PV₄W₈O₄₀; Na₉PV₆Mo₆O₄₀; Na₅CuPW₁₁O₃₉; Na₅CuPW₁₁O₄₀;Na₅MnPW₁₁O₄₀; K₅CoPW₁₁O₃₉; (ndec₄)₆HMnNb₃P₂W₁₅O₆₂; or K₁₂Cu₃(W₉PO₃₄)₂,and (2) the gold compound is HAuCl₄.
 42. The composition of claim 1,wherein the topical carrier comprises a perfluorinated polymer.
 43. Thecomposition of claim 1, wherein the topical carrier comprises aperfluorinated polymer and at least one unfluorinated polymer.
 44. Thecomposition of claim 1, wherein the topical carrier comprises aperfluoropolyether.
 45. The composition of claim 1, wherein the topicalcarrier comprises a perfluoropolyether and at least one unfluorinatedpolyether.
 46. The composition of claim 1, wherein the polyoxometalateis from 0.01 to 95% by weight of the polyoxometalate topicalcomposition.
 47. The composition of claim 2, wherein the topical carrieris a perfluoropolyether and A is silver.
 48. A method for removing acontaminant from an environment, comprising contacting thepolyoxometalate topical composition of claim 1 with the environmentcontaining the contaminant for a sufficient time to remove thecontaminant from the environment.
 49. A method for removing acontaminant from an environment, comprising contacting thepolyoxometalate topical composition of claim 36 with the environmentcontaining the contaminant for a sufficient time to remove thecontaminant from the environment.
 50. The method of claim 48, whereinthe environment comprises the gas phase.
 51. The method of claim 48,wherein the environment comprises the liquid phase.
 52. The method ofclaim 48, wherein the contaminant comprises a chemical warfare agent.53. The method of claim 48, wherein the contaminant comprises analdehyde, an aliphatic nitrogen compound, a sulfur compound, analiphatic oxygenated compound, a halogenated compound, anorganophosphate compound, a phosphonothioate compound, aphosphorothioate compound, an arsenic compound, a chloroethyl-aminecompound, a phosgene compound, a cyanic compound, or a combinationthereof.
 54. The method of claim 48, wherein the contaminant comprisesacetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide, methylsulfide, diethyl sulfide, diethyl disulfide, dimethyl sulfide, dimethyldisulfide, trimethylamine, styrene, propionic acid, n-butyric acid,n-valeric acid, iso-valeric acid, pyridine, formaldehyde, 2-chloroethylethyl sulfide, carbon monoxide, or a combination thereof.
 55. The methodof claim 48, wherein when the environment is the gas phase, thecontaminant is removed from the gas phase at from −50° C. to 250° C. andat a pressure of from ppb to 30 atm.
 56. The method of claim 48, whereinwhen the environment is the gas phase, the contaminant is removed fromthe gas phase at from 0° C. to 105° C. and at 1 atm.
 57. A method forremoving a contaminant from an environment, comprising contacting apolyoxometalate powder or a polyoxometalate coating with the environmentcontaining the contaminant for a sufficient time to remove thecontaminant from the environment.
 58. A modified polyoxometalate,wherein the modified polyoxometalate comprises the admixture of (1) apolyoxometalate and (2) a cerium compound, a silver compound, a goldcompound, a platinum compound, or a combination thereof.
 59. Themodified polyoxometalate of claim 58, wherein (1) the pre-modifiedpolyoxometalate is H₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀;K₅PV₂Mo₁₀O₄₀, or a combination thereof, and (2) the cerium compound is(NH₄)₂Ce(NO₃)₆.
 60. The modified polyoxometalate of claim 58, wherein(1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀;Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or a combination thereof; (2) the ceriumcompound is (NH₄)₂Ce(NO₃)₆; and (3) the gold compound is HAuCl₄.
 61. Themodified polyoxometalate of claim 58, wherein (1) the pre-modifiedpolyoxometalate is H₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀;K₅PV₂Mo₁₀O₄₀, or a combination thereof; (2) the cerium compound is(NH₄)₂Ce(NO₃)₆; and (3) the platinum compound is H₂PtCl₆.
 62. Themodified polyoxometalate of claim 58, wherein (1) the pre-modifiedpolyoxometalate is H₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀;K₅PV₂Mo₁₀O₄₀, or a combination thereof, and (2) the silver compound isAgNO₃.
 63. The modified polyoxometalate of claim 58, wherein (1) thepre-modified polyoxometalate independently comprises Na₄PVMo₁₁O₄₀;Na₅PV₂Mo₁₀O₄₀; Na₆PV₃Mo₉O₄₀; Na₅H₂PV₄W₈O₄₀; Na₉PV₆Mo₆O₄₀; Na₅CuPW₁₁O₃₉;Na₅CuPW₁₁O₃₉; Na₅MnPW₁₁O₄₀; K₅CoPW₁₁O₃₉; (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂; orK₁₂Cu₃(W₉PO₃₄)₂, and (2) the gold compound is HAuCl₄.
 64. Apolyoxometalate comprising K₈Co₂W₁₁O₃₉; K₈SiCoVW₁₀O₃₉; K₇SiCoVW₁₀O₃₉;Ag₅PV₂Mo₁₀O₄₀; Ag₆PV₃Mo₉O₄₀; Ag₈CoVW₁₁O₄₀; or Ag₁₂Ce(PW₁₁O₃₉)₂.
 65. Amodified material for removing a contaminant from an environment,wherein the modified material comprises (1) a material comprising atopical carrier, a powder, a coating, or a fabric, and (2) a metalcompound comprising a transition metal compound, an actinide compound, alanthanide compound, or a combination thereof, wherein the metalcompound is not a polyoxometalate.
 66. The modified material of claim65, wherein the metal compound comprises a cerium compound, a platinumcompound, a silver compound, a gold compound, or a combination thereof.67. The modified material of claim 65, wherein the metal compound is agold compound.
 68. The modified material of claim 65, wherein the metalcompound is a platinum compound.
 69. The modified material of claim 65,wherein the metal compound is a cerium compound.
 70. The modifiedmaterial of claim 65, wherein the metal compound is a silver compound.71. The modified material of claim 65, wherein the metal compound is acerium compound and a platinum compound.
 72. The modified material ofclaim 65, wherein the metal compound is a cerium compound and a goldcompound.
 73. The modified material of claim 65, wherein the metalcompound is a silver compound and a gold compound.
 74. The modifiedmaterial of claim 65, wherein the material is a topical carrier and themetal compound is a silver compound.
 75. The modified material of claim65, wherein the topical carrier is a perfluoropolyether and the metalcompound is a silver compound, a gold compound, or a combinationthereof.
 76. The modified material of claim 65, wherein the topicalcarrier is a perfluoropolyether and the silver compound is AgNO₃,AgClO₄, or a combination thereof.
 77. The modified material of claim 65,wherein the metal compound comprises (1) gold, copper, and nitrate; (2)gold, iron, and nitrate; (3) gold, manganese, and nitrate; (4) gold,titanium, and nitrate; (5) gold, cobalt, and nitrate; (6) gold andnitrate; (7) copper and nitrate; (8) iron and nitrate; (9) gold,vanadium, and nitrate; (10) gold, nickel, and nitrate; (11) gold,silver, and nitrate; (12) gold, chloride, and nitrate; or (13) ceriumcompound.
 78. The modified material of claim 65, wherein the metalcompound comprises gold, chloride, and nitrate.
 79. The modifiedmaterial of claim 65, wherein the metal compound comprises mixing (1)(NEt₄)AuCl₂ and (2) CuSO₄, MnSO₄, VOSO₄, Ti(SO₄)₂, Fe₂(SO₄)₃, NiSO₄,ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄, Pd(NO₃)₄, Na₂SO₃, or NBu₄NO₃, or acombination thereof.
 80. An article comprising the modified material ofclaim
 65. 81. A method for removing a contaminant from an environment,comprising contacting a modified material of claim 65 with theenvironment containing the contaminant for a sufficient time to removethe contaminant from the environment.